ISSN 2070-2051, Protection of Metals and Physical Chemistry of Surfaces

© Pleiades Publishing, Ltd., 2018.

PHYSICOCHEMICAL PROBLEMS
OF MATERIALS PROTECTION

Quantum Chemical Investigation of the Relationship Between

Molecular Structure and Corrosion Inhibition Efficiency
of Benzotriazole and its Alkyl-Derivatives on Iron1
Kürşat Efila, * and I. B. Obotb, **
aOndokuz
Mayis University, Faculty of Arts and Sciences, Department of Chemistry, Samsun, 55139 Turkey
b
Centre of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran,
31261 Saudi Arabia
*e-mail: kursatefil@gmail.com
**e-mail: obot@kfupm.edu.sa
Received November 15, 2016

Abstract⎯In this study, we have investigated possible role as iron corrosion inhibitor of four benzotriazole
derivatives, BTA, BTA-C1, BTA-C4, BTA-C6, using DFT calculations at B3LYP/6-311G** level of theory. For
this purpose, we have determined some structural and electronic parameters such as HOMO and LUMO
orbital energies, energy gap, electron affinity, ionization potential, hardness, softness, absolute electronega-
tivity, chemical potential, electrophilicity index, fractions of electrons transferred and back donation, logP,
molecular surface area, polar surface area, molecular volume, molar refractivity and have compared with
experimental literature results. We have also computed and discussed the interaction energy of the inhibitors
with iron surface. The calculated parameters are closely related to the inhibition efficiencies, and have com-
pared with experimental literature values using linear regression analysis to determine the most effective
parameters on inhibition efficiency.

Keywords: corrosion inhibition, benzotriazoles, HOMO-LUMO, DFT calculations, iron

DOI: 10.1134/S2070205118010215

1. INTRODUCTION 1,2,3-Benzotriazole (BTA) is one of the most

Corrosion is a crucial worldwide issue that strongly
affects natural and industrial environments [1]. Every
year billions of dollars are lost because of the corrosion
of iron and steel. Hence, this important issue has
attracted the attention of many investigators and
researchers. There are different ways to protect metals
against corrosion. One of the most simple and practi-
cal ways is the use of inhibitors [2, 3]. The selection of
effective inhibitors is dependent on electron donating
properties and their action mechanism [4]. The most
efficient inhibitors are organic compounds having π
bonds and electronegative functional groups in their
molecular structures. The anticorrosive properties of
organic molecules are mainly depend on their ability
to get on a metal surface which consists of the replace-
ment of water molecules at the corroding interface [5, 6].
Research and development of new and powerful
organic inhibitors have been of major importance
these days. Thus, the main objective of these
researches is to understand how electronic and molec-
ular properties influence the interaction between an
inhibitor molecule and a metal surface [7].
1 The article is published in the original.
effective corrosion inhibitors and this organic com-
pound is especially used to prevent the corrosion of
copper. The high inhibiting action of this molecule is
commonly attributed to the formation of a polymeric
coating on copper surface. The BTA also shows inter-
esting properties even towards the corrosion inhibition
of iron because it can interact also with the iron sur-
face [8–10].
Recently the quantum-chemical calculations are
performed using quantum chemical softwares, have
been used to clarify the mechanism of corrosion inhi-
bition. These calculations are very helpful in the
understanding of the relationship between the corro-
sion inhibition properties and molecular reactivity of a
wide range of organic corrosion inhibitors [4, 7]. The
theoretical studies on the anticorrosion properties of
organic compounds are increasing with each passing
day. Such studies are often on correlation between
experimental efficiencies of inhibitors and the quan-
tum-chemical calculations data. It has been reported
by several authors that there exist good agreement
between the experimental and theoretical results on
corrosion inhibition studies [11–19].

1
2 KÜRŞAT EFIL, OBOT
BTA
BTA-C1
Fig. 1. The molecular structure and abbreviations of benzotriazole derivatives.
Our aim in the present study is to investigate com-
putationally inhibitory action of benzotriazole and its
alkyl-derivatives on iron corrosion using B3LYP
method with 6-311G** basis set in the gas phase. The
corrosion inhibition properties of four benzotriazole
derivatives (Fig. 1), 1,2,3-benzotriazole (BTA),
methyl- (BTA-C1), butyl- (BTA-C4), hexyl- (BTA-
C6), in which experimental corrosion inhibition stud-
ies were performed previously [9], were investigated
theoretically. The structural and electronic parameters
like total energy, dipole moment, HOMO and LUMO
orbital (frontier molecular orbitals) energies, energy
gap, electron affinity, ionization potential, hardness,
softness, absolute electronegativity, chemical poten-
tial, electrophilicity index, fractions of electrons trans-
ferred and back donation, log of the octanol–water
partition coefficient, molecular surface area, polar
surface area, molecular volume and molar refractivity
were calculated. The local reactivity of studied inhibi-
tors has been analyzed by means of the Fukui indices.
We have also investigated interaction of four inhibitor
molecules with iron surface using molecular mechan-
ics (UFF) [20]. Furthermore, the relationships
between all these parameters were investigated by
using linear regression analysis. To our knowledge this
is the first study to compare experimental and compu-
tational corrosion inhibitory action of studied ben-
zotriazole derivatives. This effort will assist in the
future design of new effective benzotriazole corrosion
inhibitors.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
BTA-C4
BTA-C6
2. COMPUTATIONAL DETAILS
Theoretical calculations of four benzotriazole
derivatives as corrosion inhibitors were performed by
using the Density Functional Theory (DFT) with the
B3LYP [21] method with 6-311G** basis set imple-
mented in Gaussian 03 program package [22]. In this
work, we calculated some structural and electronic
parameters to estimate the corrosion inhibition activi-
ties of these benzotriazoles. Total energy (ET) and
dipole moment (DM) values of studied inhibitors were
obtained from the optimization and frequency calcu-
lations. The calculated parameters also obtained for
studied molecules were HOMO and LUMO orbital
(the frontier molecular orbital) energies, energy gap
(EG = EH – EL), electron affinity (EA), ionization
potential (IP), hardness (η), softness (S), absolute
electronegativity (χ), chemical potential (μ), electro-
philicity index (ω), fractions of electrons transferred
(ΔN) and back donation (ΔEB-d). All these parameters
were calculated using HOMO and LUMO orbital
analysis results. Also, the electron affinity (EAa) and
ionization potential (IPa) values for studied benzotri-
azoles were calculated independently from HOMO
and LUMO orbital energies.
The optimized molecular structures of studied
benzotriazoles were analyzed in VEGA ZZ software
[23] to determine the log of the octanol–water parti-
tion coefficient (logP), molecular surface area
(MSA), polar surface area (PSA), molecular volume
(MV) and molar refractivity (MR). The inhibition
 QUANTUM CHEMICAL INVESTIGATION
efficiency of organic compounds is dependent on
these descriptors [24, 25].
The local reactivity of studied inhibitors has been
analyzed by means of the Fukui indices [26, 27], since
they indicate the reactive regions, in the form of the
nucleophilic and electrophilic behaviour of each atom
in the molecule.
In addition to all these, we investigated interaction
of studied benzotriazoles (inhibitors) with iron (Fe)
surface using the molecular dynamics simulations.
The IP and EA are related to the energies of
HOMO and LUMO, respectively in framework of
Koopmans’ theorem [28].
IP = −E H,   (1)
EA = −E L . (2)
The global reactivities include χ, μ, η and S can
determine from the calculated IP and EA [29]. They
can be calculated from the following equations:
χ = −μ = IP + EA , (3)
2 between a cation and a neutral molecule/atom (9).
η = IP − EA , (4)
2 and it is computed as the energy difference between
S = 1. (5)
η
The electrophilicity (ω) has been introduced by
Parr et al. [30], is a descriptor of reactivity that allows
a quantitative classification of the global electrophilic
nature of a compound within a relative scale. These
scientists have proposed the ω as a measure of energy
lowering because of maximal electron flow between
donor and acceptor and defined ω as follows.
μ
2
ω= . (6)
2η
The electrons flow from a molecule with the lower
electronegativity (an organic inhibitor) to higher elec-
tronegativity (a metallic surface) for a reaction of two
systems with different electronegativity until the
chemical potential becomes equal [31]. Thus, the frac-
tion of transferred electrons (ΔN) from an inhibitor
molecule to a metallic atom was estimated according
to Pearson [32].
χ Fe − χ inh
ΔN = . (7)
[2 (ηFe +  ηinh )]
From the equation 7, the χFe and χinh denote abso-
lute electronegativity and the ηFe and ηinh denote the
absolute hardness of Fe and the inhibitor molecule,
respectively. In this work, we used the theoretical val-
ues of the χFe = 7.0 eV/mol and ηFe = 0 eV/mol by
assuming that for a metallic bulk IP = EA because they
are softer than the neutral metallic atoms [33, 34].
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
3
An electronic back-donation (ΔEB-d) process might
be occurring governing the interaction between a
metal surface and an inhibitor molecule according to
the simple charge transfer model for donation and
back-donation of charges [35]. The concept estab-
lishes that if both processes occur (namely charge
transfer to the molecule and back-donation from the
molecule) the energy change is directly proportional
to the hardness of the molecule as shown below in (8).
η
Δ E B-d = − . (8)
4
The ΔEB-d implies that when η > 0 and ΔEB-d < 0
the charge transfer to a molecule, followed by a back-
donation from the molecule, is energetically preferred.
In this context, it is possible to compare the stabiliza-
tion among inhibiting molecules, since there will be an
interaction with the same metal; then, it is expected
that it will decrease as the hardness increases.
Ionization potential (IP) is defined as the amount
of energy required to remove an electron from a mole-
cule/atom and it is computed as the energy difference
Electron affinity (EA) is defined as the energy released
when an electron is added to a neutral molecule/atom
the neutral and the anion form (10) [36, 37].
M  → M + +  e −      Δ H rxn = IP, (9)
M +  e − → M −       Δ H rxn = −EA. (10)
The ionization potential (IP) could be divided into
the vertical (IPv) and the adiabatic ionization potential
(IPa). In the same way, the electron affinity (EA) could
be divided into the vertical (EAv) and the adiabatic
electron affinity (EAa) [38]. In this work, the calcu-
lated adiabatic IP, is obtained as the energy difference
between the neutral benzotriazole molecules and the
positive molecular ions under their respective opti-
mized geometries. In the same way, calculated adia-
batic EA, is obtained as the energy difference between
the neutral benzotriazole molecules and the negative
molecular ions under their respective optimized
geometries.
The local selectivity of a corrosion inhibitor is best
analyzed by means of condensed Fukui function [39].
Their values are used to identify which atoms in the
inhibitors are more prone to undergo an electrophilic
or a nucleophilic attack.
f k+ = qk(N1)qk (N) (for nucleophilic attack), (11)
f k− = qk(N)qk(N1) (for electrophilic attack), (12)
where qN, qN + 1 and qN – 1 are the electronic popula-
tion of the atom k in neutral, anionic and cationic sys-
tems.
4 KÜRŞAT EFIL, OBOT

Table 1. Some chemical parameters of BTA, BTA-C1, indicate high nucleophilicity and the high values of s–
BTA-C4 and BTA-C6 molecules calculated with B3LYP indicate high electrophilicity.
method with 6-311G** basis set
Modeling the interaction between corrosion inhib-
Parameters BTA BTA-C1 BTA-C4 BTA-C6 itor molecules and iron metal was performed using
ET, a.u. –395.858 –435.158 –553.045 –631.634 universal force field (UFF) method [20]. Determina-
tion of this interaction energy has a very important
EH, eV –6.826 –6.737 –6.703 –6.696 place to estimate the inhibitory activity. For the deter-
EL, eV –1.450 –1.307 –1.324 –1.321 mination of this interaction energy (Eint), the energy of
EGap, eV 5.376 5.429 5.379 5.375 the iron surface (Esur) and the inhibitory molecule
(Einh), and their status as a combination (Etot) should
DM, D 3.988 4.384 4.482 4.520
be determined. After this point, the interaction energy
IP, eV 6.826 6.737 6.703 6.696 can be determined using the following equation.
EA, eV 1.450 1.307 1.324 1.321
χ, eV 4.138 4.022 4.013 4.009
E int = E tot  − ( E sur  +  E inh  ) . (16)
ƞ, eV 2.688 2.715 2.689 2.688 The binding energy of the inhibitor molecule is the
S, eV–1 0.372 0.368 0.372 0.372 negative value of the interaction energy.
μ, eV –4.138 –4.022 –4.013 –4.009 E bin = −E int . (17)
ω, eV 3.185 2.979 2.994 2.990
In this study, the calculated quantum chemical and
ΔN 0.532 0.548 0.555 0.556 structural parameters of the studied molecules were
ΔEB-d, eV –0.672 –0.679 –0.672 –0.672 compared with their experimental corrosion inhibitor
logP 1.543 1.962 3.415 4.3626 activities. As a result, we observed that there are rela-
tionships between some parameters and experimental
MSA, Å2 270.90 301.30 402.60 459.20 corrosion inhibition activities of studied molecules.
PSA, Å2 97.50 102.30 99.40 100.10 These relationships were determined with regression
104.20 116.90 171.20 202.20
analyzes and they expressed as the correlation coeffi-
MV, Å3 cient (r). All statistical analysis was performed using
MR 37.55 43.46 57.30 66.53 GNU PSPP Statistical Analysis Software version 3.0 [41].
IE, %* 69 75 93 95
* The experimental values obtained from Ref [9]. 3. RESULTS AND DISCUSSION
3.1. Quantum Chemical Study
A dual descriptor (∆f) [40] is defined as the differ- of the Inhibitors Global Reactivity
ence between the nucleophilic and electrophilic fukui
functions and is given as follows: The FMOs (HOMO and LUMO) are very import-
ant for describing chemical reactivity. The HOMO
Δf = f k+ f k−. (13) containing electrons, represents the ability (EH) to
donate an electron, whereas, LUMO, as an electron
If ∆f > 0, then the site is preferred for a nucleophilic acceptor orbital represents the ability (EL) to obtain an
attack, whereas if ∆f < 0, then the site could hardly be electron. The energy gap between HOMO and LUMO
sensitive to undertake a nucleophilic attack but it may determines the kinetic stability, chemical reactivity,
be preferred for an electrophilic attack. optical polarizability and chemical hardness–softness
For an atom, the local softness s can be expressed of a compound [42].
as the product of the condensed Fukui function (f) and In this work, we calculated the HOMO and LUMO
the global softness (S) as follows. orbital energies by using B3LYP method with
s+ = (f +)S (for nucleophilic attack), (14) 6-311G**. All other calculations were performed using
the results with some assumptions. The higher values
s– = (f –)S (for electrophilic attack). (15) of EH indicate an increase for the electron donor and
this means a better inhibitory activity with increasing
The local softness contains additional information adsorption of the inhibitor molecule on a metal sur-
about the total molecular softness, which is related to face, whereas EL indicates the ability to accept elec-
the chemical reactivity. tron of the molecule. The adsorption ability of the
The local softness contains information like those inhibitor molecule to the metal surface increases with
obtained from the condensed Fukui function and also increasing of EH and decreasing of EL. The HOMO
has additional information about the total molecular and LUMO orbital energies and images of BTA, BTA-
softness, which is related to the global reactivity with C1, BTA-C4 and BTA-C6 were performed and were
respect to the reactive agents. The high values of s+ shown in Table 1 and Fig. 2.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 QUANTUM CHEMICAL INVESTIGATION
BTA BTA-C1
HOMO
LUMO
B3LYP/6-311G**
Fig. 2. FMOs of BTA, BTA-C1, BTA-C4 and BTA-C6 by B3LYP method with 6-311G** basis set.
The optimized molecular structures of studied
benzotriazoles were analyzed in VEGA ZZ software
[23] to determine the log of the octanol–water parti-
tion coefficient (logP), molecular surface area (MSA),
polar surface area (PSA), molecular volume (MV) and
molar refractivity (MR). The inhibition efficiency of
organic compounds is dependent on these descriptors
[24, 25].
The energy gap (EGap) between HOMO and
LUMO has generally great importance in understand-
ing the static molecular reactivity. Large values of the
EGap indicate high electronic stability resulting in low
reactivity, when low values imply that it will be easier
to excite one electron from HOMO to LUMO which
can result in good inhibition efficiency. The EGap val-
ues calculated from the energy difference between EH
and EL are shown in Table 1.
The ionization potential (IP) of atoms and mole-
cules is a fundamental descriptor of the chemical reac-
tivity. The high IP means high stability and chemical
inertness and small IP means low stability and high
reactivity of the atoms and molecules [43]. The BTA-
C6 inhibitor, has lowest IP (6.696 eV), indicates the
high IE.
The dipole moment (DM) of a molecule is another
important electronic parameter which provides the
information on the polarity and the reactivity indica-
tor. The calculated results show that BTA-C6 has the
highest value of dipole moment 4.520 D with respect
to BTA-C4, BTA-C1 and BTA with values of 4.482,
4.384 and 3.988 D, respectively. From here, it can
assume that the adsorption of BTA-C6 onto the metal-
lic surface will be stronger than other molecules, and
thus the corresponding inhibition efficiencies of these
molecules will follow the order BTA-C6 > BTA-C4 >
BTA-C1 > BTA.
According to Sanderson’s electronegativity equal-
ization principle [44], BTA has a high electronegativ-
ity and low difference of electronegativity quickly
reaches equalization. Therefore, low reactivity is
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
5
BTA-C4 BTA-C6
expected which in turn indicates low inhibition. From
Table 1, the order of electronegativity (χ) is seen as
BTA > BTA-C1 > BTA-C4 > BTA-C6. Thus, an
increase in the difference of electronegativity between
the inhibitor and the metal is determined in the order
BTA-C6 > BTA-C4 > BTA-C1 >BTA.
Global hardness (η) and global softness (S) are the
basic chemical concepts, called global reactivity
descriptors. A soft molecule is more reactive than the
hard one because it could easily offer electrons to an
acceptor. In a corrosion system, the inhibitor acts as a
Lewis base while the metal acts as a Lewis acid. Bulk
metals are soft acids and thus soft base inhibitors are
most effective for acidic corrosion of those metals
[45]. From Table 1, we can see that both η and S values
of inhibitors are close to each other and thus we can-
not compare them with each other. The BTA-C1
inhibitor has highest hardness and thus is expected to
be the least reactive. However, the BTA inhibitor has
lowest reactivity as experimental. Therefore, η and S
values did not give us enough information for this
study.
The values of ΔN and ΔEB-d were also calculated
and shown in Table 1. The ΔN describes the trend of
electrons donation within a set of inhibitors. From
Lukovits’s study [46], if ΔN < 3.6 then the inhibition
efficiency increased with increasing electron-donating
ability at the mild steel/electrolyte interface. The cal-
culated values of ΔN shown in Table 1 are all below 3.6
and BTA-C6 inhibitor has higher value of ΔN than the
others. This result implies good disposition of BTA-C6
inhibitor to donate their electrons leading to increase
their adsorption on the metal surface and to increase
their inhibition efficiencies. We cannot compare the
values of ΔEB-d, related to global hardness, with each
other because they are close to each other.
The logP, MSA, PSA, MV and MR are important
molecular descriptors. They were calculated and were
given in Table 1. Here, it seems that the values of logP,
6 KÜRŞAT EFIL, OBOT

Table 2. Electronic energies of benzotriazoles obtained at 5, 6, 7 and 8 respectively and were showed the results
the B3LYP/6-311G** level in Table 3.
Electronic energies (hartrees) We can see that there is a negative correlation
between IPa and IE (Table 3). The BTA-C6, has lowest
inhibitor charge 0 charge −1 charge +1
IPa, indicates the highest IE, whereas the BTA, has
BTA –395.858 –395.851 –395.538 highest IPa, indicates the lowest IE. The IE increased
BTA-C1 –435.158 –435.151 –434.845 with decreasing IPa and thus IE values of these
BTA-C4 –553.045 –553.040 –552.738 molecules followed the order BTA-C6 > BTA-C4 >
BTA-C1 > BTA.
BTA-C6 –631.634 –631.632 –631.332
We observed that there is a negative correlation
between EAa and IE (Table 3), whereas there was no
Table 3. Global descriptors for benzotriazoles obtained at correlation for EA obtained from LUMO. The BTA-
the B3LYP/6-311G** level according to equations (1)–(8) C6, has lowest EAa, indicating the highest IE, whereas
Parameters BTA BTA-C1 BTA-C4 BTA-C6 the BTA, has highest EAa, indicating the lowest IE.
The IE increased with decreasing EAa and thus IE val-
IPa, eV 8.708 8.517 8.354 8.218 ues of these molecules followed the order BTA-C6 >
EAa, eV 0.190 0.180 0.136 0.054 BTA-C4 > BTA-C1 > BTA.
χa, eV 4.449 4.349 4.245 4.136 From Table 3, the order of χ, ƞ, ω of inhibitor mol-
ecules is seen as BTA > BTA-C1 > BTA-C4 > BTA-C6.
ƞa, eV 4.259 4.168 4.109 4.082
We can see that there is a negative correlation between
Sa, eV–1 0.235 0.240 0.243 0.245 χ, ƞ, ω and IE. The IE increased with decreasing χ, ƞ,
μa, eV –4.449 –4.349 –4.245 –4.136 ω and thus IE of these molecules followed the order
BTA-C6 > BTA-C4 > BTA-C1 > BTA.
ωa, eV 2.324 2.269 2.193 2.096
The order of S, μ, ΔEB-d of inhibitor molecules was
ΔNa 0.300 0.318 0.335 0.351 found as BTA-C6 > BTA-C4 > BTA-C1 > BTA. It can
ΔE(B-d)a, eV –1.065 –1.042 –1.027 –1.020 be seen that there is a positive correlation between S,
IE, %* 69 75 93 95 μ, ΔEB-d and IE. The IE increased with increasing S,
μ, ΔEB-d and thus IE of these molecules followed the
* The experimental values obtained from Ref [9]. order BTA-C6 > BTA-C4 > BTA-C1 > BTA.

MSA, MV and MR have a positive correlation with Local Reactivity

experimental IE (%) whereas PSA has no correlation.
The energy values of the ionic states (cation and
anion) of studied benzotriazoles were calculated by
using the geometry of the neutral system (Table 2).
The energy value of the adiabatic electronic affinity
(EAa) was obtained as EAa = E(N) − E(N − 1) where
E(N) and E(N − 1) are the total ground-state energies
in the neutral N and singly charged (N − 1) configura-
tions. In a similar way, the adiabatic ionization poten-
tial (IPa) was obtained as IPa = E(N + 1) − E(N).
In addition, the values of χa, μa, ƞa, Sa, ωa, ΔNa and
ΔE(B-d)a were calculated employing the equations 3, 4,
The local reactivity of the inhibitors was analyzed
by means of the Fukui indices, because they are indic-
ative of the reactive regions, as well as the nucleophilic
and electrophilic behavior of each inhibitor molecules.
Therefore, Fukui indices can be used to analyze the
local selectivity of a corrosion inhibitor [47].
The calculated Fukui functions using the Mulliken
population analysis (MPA) for the inhibitors are pre-
sented in Table 4 and the numbered atoms on ben-
zotriazole core are shown in Fig. 3. According to fukui
indices, N(2) is the most reactive site for nucleophilic
attack for all inhibitors and N(3) for BTA and C(8) for
others are the site of electrophilic attack.

Interaction Between Studied Inhibitors

8 and Iron Surface
9
1
7 When an inhibitor and Fe surface interact, a certain
2 part of energy will decrease and this decreased energy
6
corresponds to the interaction energy (Eint) between
4
3 5 them. The Eint can be determined by the difference
between the energy of the system (inhibitor-Fe) and
the sum of energy of individual inhibitor and Fe sur-
Fig. 3. The numbered atoms on benzotriazole core. face. The larger negative values of interaction energy

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 QUANTUM CHEMICAL INVESTIGATION 7

Table 4. Mulliken atomic charges, Fukui indices, dual descriptors and local softness indices for nucleophilic and electro-
philic attacks for atoms of the inhibitor molecules
Inhibitor Atom N N+1 N–1 q(N) q(N + 1) q(N – 1) f k+ f k− Δf s+ s–

BTA N (1) –0.362 –0.331 –0.403 7.362 7.403 7.331 0.041 0.031 0.010 0.010 0.007
N(2) –0.007 0.092 –0.180 7.007 7.180 6.908 0.173 0.099 0.074 0.041 0.023
N(3) –0.235 –0.133 –0.323 7.235 7.323 7.133 0.088 0.102 –0.014 0.021 0.024
C(4) –0.008 –0.003 0.008 6.008 5.992 6.003 –0.016 0.005 –0.021 –0.004 0.001
C(5) –0.030 0.070 –0.157 6.030 6.157 5.930 0.127 0.100 0.027 0.030 0.023
C(6) –0.104 –0.025 –0.115 6.104 6.115 6.025 0.011 0.079 –0.068 0.003 0.019
C(7) –0.101 –0.068 –0.157 6.101 6.157 6.068 0.056 0.033 0.023 0.013 0.008
C(8) –0.041 0.058 –0.153 6.041 6.153 5.942 0.112 0.099 0.013 0.026 0.023
C(9) 0.232 0.305 0.219 5.768 5.781 5.695 0.013 0.073 –0.060 0.003 0.017
BTA-C1 N (1) –0.369 –0.302 –0.408 7.369 7.408 7.302 0.039 0.067 –0.028 0.009 0.016
N(2) –0.012 0.092 –0.175 7.012 7.175 6.908 0.163 0.104 0.059 0.039 0.025
N(3) –0.236 –0.171 –0.320 7.236 7.320 7.171 0.084 0.065 0.019 0.020 0.016
C(4) –0.007 0.047 0.006 6.007 5.994 5.953 –0.013 0.054 –0.067 –0.003 0.013
C(5) –0.025 0.061 –0.154 6.025 6.154 5.939 0.129 0.086 0.043 0.031 0.021
C(6) –0.090 –0.047 –0.097 6.090 6.097 6.047 0.007 0.043 –0.036 0.002 0.010
C(7) –0.117 –0.095 –0.115 6.117 6.115 6.095 –0.002 0.022 –0.024 0.000 0.005
C(8) –0.016 0.102 –0.151 6.016 6.151 5.898 0.135 0.118 0.017 0.032 0.028
C(9) 0.241 0.230 0.234 5.759 5.766 5.770 0.007 –0.011 0.018 0.002 –0.003
BTA-C4 N (1) –0.373 –0.314 –0.409 7.373 7.409 7.314 0.036 0.059 –0.023 0.009 0.014
N(2) –0.011 0.087 –0.171 7.011 7.171 6.913 0.160 0.098 0.062 0.039 0.024
N(3) –0.236 –0.177 –0.318 7.236 7.318 7.177 0.082 0.059 0.023 0.020 0.014
C(4) –0.008 0.043 0.006 6.008 5.994 5.957 –0.014 0.051 –0.065 –0.003 0.012
C(5) –0.024 0.054 –0.15 6.024 6.15 5.946 0.126 0.078 0.048 0.031 0.019
C(6) –0.078 –0.039 –0.101 6.078 6.101 6.039 0.023 0.039 –0.016 0.006 0.009
C(7) –0.099 –0.075 –0.105 6.099 6.105 6.075 0.006 0.024 –0.018 0.001 0.006
C(8) –0.018 0.097 –0.134 6.018 6.134 5.903 0.116 0.115 0.001 0.028 0.028
C(9) 0.248 0.241 0.235 5.752 5.765 5.759 0.013 –0.007 0.02 0.003 –0.002
BTA-C6 N (1) –0.373 –0.318 –0.409 7.373 7.409 7.318 0.036 0.055 –0.019 0.008 0.013
N(2) –0.011 0.084 –0.171 7.011 7.171 6.916 0.160 0.095 0.065 0.034 0.023
N(3) –0.236 –0.180 –0.318 7.236 7.318 7.180 0.082 0.056 0.026 0.017 0.014
C(4) –0.009 0.042 0.006 6.009 5.994 5.958 –0.015 0.051 –0.066 –0.003 0.012
C(5) –0.024 0.049 –0.150 6.024 6.150 5.951 0.126 0.073 0.053 0.027 0.018
C(6) –0.078 –0.041 –0.101 6.078 6.101 6.041 0.023 0.037 –0.014 0.005 0.009
C(7) –0.100 –0.079 –0.106 6.100 6.106 6.079 0.006 0.021 –0.015 0.001 0.005
C(8) –0.018 0.092 0.134 6.018 5.866 5.908 –0.152 0.110 –0.262 –0.032 0.027
C(9) 0.248 0.242 0.235 5.752 5.765 5.758 0.013 –0.006 0.019 0.003 –0.001

indicate favorable interaction between inhibitor mole- (110) surface to find out the most low energy adsorp-
cules and Fe surface [48]. tion sites along with their suitable configuration. The
In this study, four selected inhibitors (BTA, BTA- Eint between inhibitor molecules and Fe (110) surface
C1, BTA-C4 and BTA-C4) have been placed on the Fe can be calculated using the Eq. (16) by single point

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

8 KÜRŞAT EFIL, OBOT

Table 5. Interaction energies (kcal/mol) between studied (interaction and binding energies) were presented in
inhibitors and Fe surface calculated at UFF method in gas Table 5 and they are all in good agreement with the
phase results obtained from experimental work [9]. Also,
Stracture Eint Ebin adsorption configurations of the studied inhibitors on
Fe (110) surface are shown in Fig. 4.
BTA…Fe –0.0774 0.0774
BTA-C1…Fe –0.0933 0.0933
BTA-C4…Fe –0.1389 0.1389 3.2. Correlation Study Between Corrosion Inhibition
BTA-C6…Fe –0.1648 0.1648
Efficiencies and Some Parameters
The correlation coefficient (r) is a way to measure
the strength of the relationship between two variables.
energy calculation. The calculated Eint values of the Hence, we determined values of r for all parameters.
adsorption systems were –0.0774, –0.0933, –0.1389 Obtained theoretical results indicate that a weak linear
and –0.1648 kcal mol–1 for BTA, BTA-C1, BTA-C4 relationship was found between PSA (r = 0.15) and
and BTA-C6, respectively. The calculated results inhibition efficiency (IE). A moderate linear relation-

Fig. 4. Adsorption configurations of the studied inhibitors on Fe (110) surface obtained by UFF.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 QUANTUM CHEMICAL INVESTIGATION 9

–3 4.6 6.9 6

–4 4.4 6.8 4
ET ×102

log P
DM

IP
–5 4.2
6.7 2
–6 4.0
–7 3.8 6.6 0
65 75 85 95 65 75 85 95 65 75 85 95 65 75 85 95
IE, % IE, % IE, % IE, %
500 250 70 8.8
200 60
400 8.6
MSA

MV

IPa
150 50

MR
300 8.4
100 40
200 50 30 0
65 75 85 95 65 75 85 95 65 75 85 95 65 75 85 95
IE, % IE, % IE, % IE, %
0.26 0.18 –0.06

0.17 –0.10
fk+(N(2))

0.18
EAa

Eint
0.10 0.16 –0.14

0 0.15 –0.18
65 75 85 95 65 75 85 95 65 75 85 95
IE, % IE, % IE, %

Fig. 5. Correlation graphs between important parameters and IE.

ship was detected between EG, ƞ, S, ΔEB-d (r = 0.39)
and IE. The values of r greater than 0.5 is generally
described as strong and there was a strong linear rela-
tionship between EA (r = 0.64) and IE. For parameters
with r values greater than 0.7 was created a correlation
matrix table (Table 5).
From Table 6, we can see that there is reasonably
good (r > 0.7) linear relationship for χ and μ, good
(r > 0.9) linear relationship for ET, DM, IP, ΔN, logP,
MSA, MV, MR, IPa, EAa, χa, ƞa, Sa, μa, ωa, ΔNa,
ΔE(B-d)a, f k (+N (2)), Eint with experimental IE.
When these relationships are evaluated, indepen-
dent parameters ET, DM, IP, logP, MSA, MV, MR, IPa,
EAa, f k (+N (2)), Eint have an important role to estimate
the corrosion protection properties of corresponding
molecules. The relationship graphs between these
parameters and experimental IE are shown Fig. 5.
4. CONCLUSION
Density functional theory at the DFT/B3LYP/6-
311G** level of theory was performed to study the
inhibition efficiency and the adsorption mechanisms
of four benzotriazoles used as corrosion inhibitors for
iron. The chemical quantum parameters and the
interaction energies between the inhibitors and iron
surface were computed and analyzed. The following
conclusions could be drawn from the investigation:
1. The inhibition efficiency of studied benzotri-
azole compounds are correlated to their molecular
structure using the DFT/B3LYP/6-311G** method.
2. The global and local parameters have provided
more insights into the inhibition efficiency of studied
molecules.
3. The interaction energy between inhibitor mole-
cules and Fe (110) surface was calculated and it is
closely related with experimental IE.
4. The calculated parameters χ, μ, ET, DM, IP, ΔN,
logP, MSA, MV, MR, IPa, EAa, χa, ƞa, Sa, μa, ωa, ΔNa,
ΔE(B-d)a, fk(+N (2)) and Eint show reasonably good (r >
0.7) and very good (r > 0.9) correlation with the effi-
ciency of corrosion inhibition.
5. The correlation graphs between some important
parameters and experimental inhibition efficiency
were obtained.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 Table 6. Correlation matrix table between parameters for r = 0.7 and above
10

ET DM IP χ μ ΔN logP MSA MV MR IPa EAa χa ƞa Sa μa ωa ΔNa ΔE(B-d)a fk(+N (2)), Eint

ET 1.00

DM –0.82 1.00
IP 0.85 –1.00 1.00
χ 0.73 –0.99 0.98 1.00
μ –0.73 0.99 –0.98 –1.00 1.00
ΔN –0.86 1.00 –1.00 –0.97 0.97 1.00
logP –1.00 0.81 –0.84 –0.72 0.72 0.85 1.00
MSA –1.00 0.82 –0.85 –0.73 0.73 0.86 1.00 1.00
MV –1.00 0.80 –0.84 –0.71 0.71 0.85 1.00 1.00 1.00
MR –1.00 0.84 –0.87 –0.75 0.75 0.88 1.00 1.00 1.00 1.00
IPa 0.97 –0.93 0.94 0.86 –0.86 –0.95 –0.97 –0.97 –0.97 –0.98 1.00

EAa 0.96 –0.70 0.73 0.61 –0.61 –0.74 –0.96 –0.95 –0.96 –0.96 0.91 1.00

χa 0.99 –0.89 0.91 0.82 –0.82 –0.91 –0.98 –0.98 –0.98 –0.99 1.00 0.95 1.00
KÜRŞAT EFIL, OBOT

ƞa 0.93 –0.97 0.98 0.93 –0.93 –0.99 –0.93 –0.93 –0.92 –0.94 0.99 0.84 0.97 1.00

Sa –0.94 0.97 –0.98 –0.92 0.92 0.98 0.93 0.94 0.93 0.95 –0.99 –0.86 –0.98 –1.00 1.00

μa –0.99 0.89 –0.91 –0.82 0.82 0.91 0.98 0.98 0.98 0.99 –1.00 –0.95 –1.00 –0.97 0.98 1.00

ωa 0.99 –0.84 0.86 0.76 –0.76 –0.87 –0.99 –0.98 –0.98 –0.99 0.98 0.98 0.99 0.94 –0.95 –0.99 1.00

ΔNa –0.98 0.91 –0.92 –0.84 0.84 0.93 0.98 0.98 0.97 0.99 –1.00 –0.93 –1.00 –0.98 0.98 1.00 –0.99 1.00

ΔE(B-d)a –0.93 0.97 –0.98 –0.92 0.92 0.99 0.93 0.93 0.92 0.95 –0.99 –0.84 –0.97 –1.00 1.00 0.97 –0.94 0.98 1.00

fk(+N (2)), 0.81 –1.00 1.00 0.99 –0.99 –1.00 –0.80 –0.81 –0.79 –0.83 0.91 0.67 0.87 0.97 –0.96 –0.87 0.82 –0.89 –0.96 1.00

Eint 1.00 –0.83 0.86 0.74 –0.74 –0.87 –1.00 –1.00 –1.00 –1.00 0.98 0.95 0.99 0.94 –0.95 –0.99 0.99 –0.98 –0.94 0.82 1.00

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

IE –0.97 0.86 –0.89 –0.78 0.78 0.90 0.97 0.98 0.97 0.97 –0.96 –0.87 –0.95 –0.95 0.95 0.95 –0.94 0.96 0.95 –0.86 –0.98
 QUANTUM CHEMICAL INVESTIGATION
ACKNOWLEDGMENTS
The authors would like to acknowledge the support
and fruitful collaboration between the Department of
Chemistry, Faculty of Science, Ondokuz Mayis Uni-
versity, Turkey and the Center of Research Excellence
in Corrosion (CORE-C), at King Fahd University of
Petroleum and Minerals (KFUPM) Saudi Arabia.
REFERENCES
1. Valdez, B., Schorr, M., Zlatev, M., et al., in Environ-
mental and Industrial Corrosion, Salas, B.V. and
Schorr, M., Eds., InTech, 2012, p. 19. doi
10.5772/51987
2. Loto, R.T., Loto, C.A., and Fedotova, T., Int. J. Elec-
trochem. Sci., 2012, vol. 7, p. 10763.
3. Wazzan, N. and Mahgoub, F., Open J. Phys. Chem.,
2014, vol. 4, p. 6.
4. El Adnani, Z., Mcharfi, M., Sfaira, M., et al., Int. J.
Electrochem. Sci.,2012, vol. 7, p. 6738.
5. Mokhtari, O., Hamdani, I., Chetouani, A., et al.,
J. Mater. Environ. Sci., 2014, vol. 5, p. 310.
6. Shivakumar, S.S. and Mohana, K.N., Int. J. Corros.,
2013, vol. 13, Art. ID 543204.
7. El Adnani, Z., Mcharfi, M., Sfaira, M., et al., Corros.
Sci., 2013, vol. 68, p. 223.
8. Arancibia, A., Henriquez-Roman, J., Páez, M.A.,
et al., J. Solid State Electrochem., 2005, vol. 10, p. 894.
9. Trabanelli, G., Frignani, A., Monticelli, C., and Zuc-
chi, F., Int. J. Corros. Scale Inhib., 2015, vol. 4, p. 96.
10. Frignani, A., Tommesani, L., Brunoro, C., et al., Cor-
ros. Sci., 1999, vol. 41, p. 1205.
11. Khaled, K.F., Babić-Samardžija, K., and Hackerman, N.,
Electrochim. Acta, 2005, vol. 50, p. 2515.
12. Costa, J.M. and Lluch, J.M., Corros. Sci., 1984, vol. 24,
p. 929.
13. El-Naggar, M.M., Corros. Sci., 2007, vol. 49, p. 2226.
14. Arslan, T., Kandemirli, F., Ebenso, E.E., et al., Corros.
Sci., 2009, vol. 51, p. 35.
15. Boussalah, N., Ghalem, S., El Kadiri, S., et al., Res.
Chem. Intermed., 2012, vol. 38, p. 2009.
16. Ebenso, E.E., Arslan, T., Kandemi̇rlı, F., et al., Int. J.
Quantum Chem., 2010, vol. 110, p. 2614.
17. Ju, H., Ding, L., Sun, C., and Chen, J., Adv. Mater. Sci.
Eng., 2014, vol. 5.
18. Efil, K. and Bekdemir, Y., Can. Chem. Trans., 2015,
vol. 3, p. 85.
19. Obot, I.B., Kaya, S., Kaya, C., and Tüzün, B., Res.
Chem. Intermed., 2016, vol. 42, p. 4963.
20. Rappe, A.K., Casewit, C.J., Colwell, K.S., et al., J. Am.
Chem. Soc., 1992, vol. 114, p. 10024.
21. Becke, A.D., J. Chem. Phys., 1993, vol. 98, p. 5648.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
11
22. Frisch, M.J., Trucks, G.W., Schlegel, H.B., et al.,
Gaussian 03, Revision E.01, Wallingford, CT: Gaussian,
2004.
23. Pedretti, A., Villa, L., and Vistoli, G., J. Mol. Graphics
Modell., 2002, vol. 21, p. 47.
24. Khaled, K.F., Corros. Sci., 2011, vol. 53, p. 3457.
25. Winkler, D.A., Breedon, M., Hughes, A.E., et al.,
Green Chem., 2014, vol. 16, p. 3349.
26. Yang, W. and Mortier, W.J., J. Am. Chem. Soc., 1986,
vol. 108, p. 5708.
27. Rodríguez-Valdez, L.M., Martínez-Villafañe, A., and
Glossman-Mitnik, D., J. Mol. Struct.: THEOCHEM,
2005, vol. 713, p. 65.
28. Koopmans, T., Physica, 1934, vol. 41, p. 104. Koop-
mans, T., Physica, 1934, vol. 1, p. 104.
29. Lesar, A. and Milošev, I., Chem. Phys. Lett., 2009,
vol. 483, p. 198.
30. Parr, R.G., Szentpály, L., and Liu, S., J. Am. Chem.
Soc., 1999, vol. 121, p. 1922.
31. Martinez, S., Mater. Chem. Phys., 2002, vol. 77, p. 97.
32. Pearson, R.G., Inorg. Chem., 1988, vol. 27, p. 734.
33. Sastri, V.S. and Perumareddi, J.R., Corrosion, 1997,
vol. 53, p. 617.
34. Lukovits, I., Kálmán, E., and Zucchi, F., Corrosion,
2001, vol. 57, p. 3.
35. Gómez, B., Likhanova, N.V., Domínguez-
Aguilar, M.A., et al., J. Phys. Chem. B, 2006, vol. 110,
p. 8928.
36. Foresman, J.B. and Frisch, A., Exploring Chemistry
with Electronic Structure Methods: A Guide to Using
Gaussian, Pittsburgh, PA: Gaussian, 1996.
37. Lias, S.G. and Bartmess, J.E., Gas-Phase Ion Thermo-
chemistry, 2016. http://webbook.nist.gov/chemistry.
38. Boldyrev, A., Simons, J., Zakrzewski, V., and von Nies-
sen, W., J. Phys. Chem., 1994, vol. 98, p. 1427.
39. Fuentealba, P., Pérez, P., and Contreras, R., J. Chem.
Phys., 2000, vol. 113, p. 2544.
40. Morell, C., Grand, A., and Toro-Labbé, A., J. Phys.
Chem. A, 2005, vol. 109, p. 205.
41. GNU, PSPP–GNU Project–Free Software Founda-
tion, 2007. https://www.gnu.org/software/pspp/.
42. Govindarajan, M. and Karabacak, M., Spectrochim.
Acta, Part A, 2012, vol. 85, p. 251.
43. Chakraborty, T., Gazi, K., and Ghosh, D.C., Mol.
Phys., 2010, vol. 108, p. 2081.
44. Geerlings, P. and De Proft, F., Int. J. Mol. Sci., 2002,
vol. 3, p. 276.
45. Kayadibi, F., Sagdinc, S.G., and Kara, Y.S., Prot. Met.
Phys. Chem. Surf., 2015, vol. 51, p. 143.
46. Lukovits, I., Kálmán, E., and Zucchi, F., Corrosion,
2001, vol. 57, p. 3.
47. Udhayakala, P., Samuel, A.M., Rajendiran, T.V., and
Gunasekaran, S., Pharma Chem., 2013, vol. 5, p. 111.
48. Hizaddin, H.F., Anantharaj, R., and Hashim, M.A.,
J. Mol. Liq., 2014, vol. 194, p. 20.