Corrosion Science 52 (2010) 657–660

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Short Communication

Theoretical study of benzimidazole and its derivatives and their potential activity
as corrosion inhibitors
I.B. Obot a,*, N.O. Obi-Egbedi b
a
Department of Chemistry, Faculty of Science, University of Uyo, Uyo, Nigeria
b
Department of Chemistry, University of Ibadan, Ibadan, Nigeria

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

Article history: A theoretical study of benzimidazole (BI) and two of its derivatives namely 2-methylbenzimidazole (2-
Received 27 June 2009 CH3BI) and 2-mercaptobenzimidazole (2-SHBI) recently used as corrosion inhibitors for mild steel in
Accepted 9 October 2009 1 M HCl was undertaken by considering Density Functional Theory (DFT) at the B3LYP/6-311G++(d,p)
Available online 17 October 2009
level. The properties most relevant to their potential action as corrosion inhibitors has been calculated
in the neutral and protonated form: EHOMO, ELUMO, energy gap (DE), dipole moment (l), electronegativity
Keywords: (v), global hardness (g) and the fraction of electrons transferred from the inhibitor molecule to the metal-
A. Mild steel
lic atom (DN). The theoretical results are in agreement with the experimental data.
B. Benzimidazole
C. Acid corrosion
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction
Organic inhibitors generally protect the metal from corrosion by
forming a film on the metal surface. Their effectiveness as reported
by several authors [1–4] is related to the chemical composition,
spatial molecular structure, molecular electronic structure, surface
charge density, and their affinity for the metal surface. In addition,
specific interaction between functional groups and the metal sur-
face and heteroatoms like oxygen, nitrogen, sulphur and phospho-
rus play an important role in inhibition due to the free electron
pairs they possess.
Benzimidazole is a heterocyclic aromatic organic compound.
This bicyclic compound consists of the fusion of benzene and imid-
azole. The most prominent benzimidazole compound in nature is
N-ribosyl-dimethylbenzimidazole which serves as an axial ligand
for cobalt in vitamin B12 [5]. Benzimidazole is commercially avail-
able but the usual synthesis involves condensation of o-phenylene-
diamine with formic acid [6]. By altering the carboxylic acid, this
method is generally able to afford 2-substituted benzimidazole
[6]. Benzimidazole and its derivatives play a vital role in biological
fields such as antimicrobial [7], antiviral [8], antidiabetic [9], anti-
spasmodic [10], and anticancer activities [11]. Of all the benzimid-
azole derivatives, 2-substituted benzimidazole derivatives have
been found to be biologically most potent [12]. Though, the use
of benzimidazole and its derivatives as corrosion inhibitors for
* Corresponding author. Address: Department of Chemistry, Faculty of Science,
University of Uyo, P.M.B 1017, Uyo, Akwa Ibom State, Nigeria. Tel.: +234
8067476065.
E-mail address: proffoime@yahoo.com (I.B. Obot).
mild steel in acidic media have been reported [13–15], the use of
quantum-chemical studies in probing the mechanism of inhibition
action is scanty.
Quantum-chemical calculations have been widely used to study
reaction mechanism. They have also proved to be a very important
tool for studying corrosion inhibition mechanism [16–18]. In re-
cent times, Density Functional Theory (DFT) has become an attrac-
tive theoretical method because it gives exact basic vital
parameters for even huge complex molecules at low cost. Further-
more, by using sophisticated computational tools, we can under-
stand reactivity behaviour of hard and soft acid–base (HSAB)
theory that provide a systematic way for the analysis of the inhib-
itor/surface interaction [19]. Thus, the DFT has become a main
source of connecting some traditional empirical concepts with
quantum mechanics. Therefore, DFT is a very powerful technique
to probe the inhibitor/surface interaction and to analyze experi-
mental data.
The inhibitive properties of benzimidazole (BI) and two of its
derivatives namely 2-methylbenzimidazole (2-CH3BI) and 2-mer-
captobenzimidazole (2-SHBI) have been reported in a recent exper-
imental study [20]. The inhibition efficiency was found to increase
in the order 2-mercaptobenzimidazole > 2-methylbenzimida-
zole > benzimidazole. The aim of this work therefore, is to extend
these investigations in order to ascertain vividly whether there is
a clear relationship between the calculated quantum-chemical
parameters and the experimentally determined inhibition efficien-
cies of the inhibitors. This is achieved by calculating the more
relevant molecular properties of these inhibitors and thereafter
explains the mechanism of inhibition of the inhibitors with the
mild steel surface. These properties are EHOMO, ELUMO, energy gap

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.10.017
658 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 657–660

(DE), dipole moment (l), electronegativity (v), global hardness (g)

and the fraction of electrons transferred from the inhibitor mole-
cule to the metallic atom (DN).

2. Computational details

B3LYP, a version of the DFT method that uses Becke’s three

parameter functional (B3) and includes a mixture of HF with DFT ex-
change terms associated with the gradient corrected correlation
functional of Lee, Yang and Parr (LYP) [21], was used in this paper
to carry out quantum calculations. Then, full geometry optimization
together with the vibrational analysis of the optimized structures of
all inhibitors were carried out at the highest (B3LYP/6-311G++(d,p))
level of theory using Spartan’06 V112 program package [22] in order
to determine whether they correspond to a maximum or a minimum
in the potential energy curve. The theoretical parameters were cal-
culated in gas phase, but it is well known that the phenomenon of
electrochemical corrosion appears in liquid phase. As a result, it
was necessary to include the effect of a solvent in the computational
calculations. In the Spartan ‘06 V112 program, SCRF methods (self-
consistent reaction field) were used to perform calculations in solu-
tion. These methods model the solvent as a continuum of uniform
dielectric constant and the solute is placed in the cavity within it.

3. Results and discussion

The chemical structures of the compounds under investigation

are presented in Table 1. The optimized molecular structures of
the studied molecules using hybrid DFT functional (B3LYP/6-
311G++ (d,p) are shown in Fig. 1. All the quantum-chemical param-
eters in the neutral and in the protonated forms are given in Tables
2 and 3, respectively.
It is important to note that the calculated parameters of the
neutral form of the inhibitors in gas phase as well as in the pres-
ence of a solvent do not exhibit any difference. Thus it is acceptable
to obtain results in the gaseous phase because it reduces the time
of calculation and no significant differences are found [23]. How-
ever, calculations of the protonated form were done in the solvent
phase. Moreover, from the theoretical calculations carried out with
both neutral and protonated forms of the inhibitors, high correla-
tion coefficients of the inhibition efficiencies with electronic prop-
erties was obtained with the neutral forms of the inhibitors than
with the protonated forms (Tables 2 and 3). Consequently, theoret-
ical calculations with only the neutral form of these molecules
Fig. 1. Optimized structures of the compounds: (a) benzimidazole (BI); (b) 2-
could be a good approach for the study of their potential inhibition methylbenzimidazole (2-CH3BI) and (c) 2-mercaptobenzimidazole (2-SHBI).
capability of metal corrosion in acidic media. This is acceptable

Table 1 judging from the fact that the values of DG0ads obtained from the
Molecular structures, Abbreviations and molar masses of the studied compounds experimental work lies between 28.78 and 32.77 kJ/mol [20].
from Ref. [20]. It has been reported that values of DG0ads between this range indi-
Inhibitor Structure Abbrevation Molar mass cates that adsorption may involve complex interactions: chemical
(g/mol) adsorption and physical adsorption [24]. Bayoumi and Ghanem
[25] reported that the adsorption of naphthalene disulphonic on
Benzimidazole BI 118.14
mild steel is chemisorptions ðDG0ads ¼ 28:47 kJ=molÞ. Recently,
Badiea and Mohana [26] has attributed values of DG0ads between
27.10 to 32.41 kJ/mol to chemisorptions which involves direct
adsorption on the basis of donor–acceptor interactions between
2-Methylbenzimidazole 2-CH3-BI 132.10 the lone pairs of electrons, p-electrons and the vacant d-orbitals
of iron surface atoms. Thus, the discussions of the present study fo-
cus mainly on the neutral form of the inhibitors (Table 2).
It has been found in previous works that a good correlation be-
tween corrosion inhibition efficiency and EHOMO exist. Similar rela-
2- Mercaptobenzimidazole 2-SH-BI 150.20
tions were found between corrosion inhibition efficiency and
DE = ELUMO–EHOMO [27,28]. Also there are certain quantum-chemi-
cal parameters that can be related to metal-inhibitor interactions.
 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 657–660 659

Table 2 within DFT, its validity is generally accepted. The obtained values
Quantum-chemical parameters for the neutral form of the inhibitors obtained with of I and A were considered for the calculation of the electronegativ-
the DFT at the B3LYP/6-311G++ (d,p) level.
ity (v) and global hardness (g). The fraction of electrons transferred
Quantum-chemical parameters BI 2-SHBI 2-CH3BI R2 from the inhibitor molecule to the metallic atom (DN) was calcu-
EHOMO 6.38 6.15 6.22 0.622 lated according to Pearson [36]. The idea behind this is that in
ELUMO 0.95 0.98 0.75 0.261 the reaction of two systems with different electronegativities (as
ELUMO EHOMO 5.43 5.16 5.47 0.933 a metallic surface and an inhibitor molecule) the following mech-
Dipole moment 3.60 4.30 3.71 0.999
Electronegativity (v) 3.66 3.45 3.48 0.561
anism will take place: the electron flow will happen from the mol-
Hardness (g) 2.72 2.58 2.74 0.921 ecule with the low electronegativity towards that of a higher value,
(DN) 0.61 0.69 0.64 0.956 until the chemical potentials are the same. In order to calculate the
Inhibition efficiencya 73.8 90.1 76.3 fraction of electrons transferred, a theoretical value for the electro-
a
Values from Ref [20]. negativity of bulk iron was used vFe = 7 eV [36], and a global hard-
ness of gFe = 0, by assuming that for a metallic bulk I = A [37]
because they are softer than the neutral metallic atoms. For the
Table 3 calculation the following formula was used [36]:
Quantum-chemical parameters for the protonated form of the inhibitors obtained
vFe  vinb
with the DFT at the B3LYP/6-311G++ (d,p) level. DN ¼
2ðgFe þ ginh Þ
Quantum-chemical parameters BI 2-SHBI 2-CH3BI R2
EHOMO 11.25 10.82 10.98 0.760
These quantities are related to electron affinity (A) and ioniza-
ELUMO 6.14 5.67 5.65 0.347 tion potential (I) which are useful in their ability to help predict
ELUMOEHOMO 5.11 5.14 5.34 0.046 chemical behaviour [37].
Dipole moment 4.87 2.75 4.51 0.999
Electronegativity (v) 8.69 8.24 8.32 0.548 IþA
Hardness (g)
v¼
2.55 2.57 2.67 0.049 2
(DN) 0.331 0.24 0.24 0.431
Inhibition efficiencya 73.8 90.1 76.3
IA
g¼
a
Values from Ref [20]. 2
I and A are related in turn to EHOMO and ELUMO as follows:
I ¼ EHOMO
Among these, we can mention the energy of HOMO that is often
associated with the electronic donating ability of a molecule. A ¼ ELUMO
Therefore, an increase in the values of EHOMO can facilitate the
adsorption and therefore the inhibition efficiency, by indicating From Table 2, it is possible to observe that 2-SHBI molecule has
the disposition of the molecule to donate orbital electrons to an the lowest value of global hardness while the electronegativities
appropriate acceptor with empty molecular orbitals. The energy calculated is almost similar for 2-SHBI and 2-CH3BI as compared
of LUMO on the other hand, indicates the ability of the molecule to BI which has the highest value. Thus, the fraction of transferred
to accept electrons. The lower the value of ELUMO, the more proba- electrons is largest for the 2-SHBI as compared to the other com-
ble it is that the molecule accepts electrons [29]. In the same way, pounds studied. Low hardness value and high value of the fraction
low values of the energy of the gap DE = ELUMOEHOMO will render of electron transferred enhances inhibition efficiency [38]. Thus,
good inhibition efficiencies, because the energy to remove an elec- the higher inhibition effects of 2-SHBI in comparison with BI and
tron from the last occupied orbital will be low [30]. Increasing val- 2-CH3BI may be attributed to the presence of S and N atoms at
ues of dipole moment has been reported to facilitate adsorption the same time in its molecular structure. Organic inhibitors which
(and therefore inhibition) by influencing the transport process have reactive functional groups are sites of the adsorption process.
through the adsorbed layer [29]. Meanwhile, several authors have The strength of the adsorption bond depends upon the electron
stated that inhibition efficiency increases with increasing values of density of the donor atom. The inhibition efficiency of organic
the dipole moments [31,32]. On the other hand, survey of literature compounds containing different donor atoms is in the sequence
reveals that several irregularities appeared in case of correlation of [38] S > N > O. According to Zhang et al. [39] the introduction of
dipole moment with inhibition efficiency [33,34]. mercapto group to a heterocyclic compound can vary the distur-
The results obtained by B3LYP/6-31G++ (d,p) method (Table 2) bances and orbital energy configurations of electrons, thus enhanc-
show that 2-SHBI has the highest HOMO energy (EHOMO) and the ing the inhibition. Also the greater inhibition efficiency of 2-CH3BI
lowest LUMO energy (ELUMO) among these organic heterocyclic when compared to BI is the present of methyl group (CH3). Methyl
compounds. Furthermore, it can also be seen from Table 2 that groups are electron donors and it increases electron density of 2-
2-SHBI has the smaller energy gap (DE = ELUMOEHOMO) as com- CH3BI. This further supports the experimental results.
pared to other molecules. This indicates that 2-SHBI molecule
can easily transfer an electron from HOMO level to LUMO level. 4. Conclusions
However, we remark that this difference is principally supported
by an increase of LUMO energy of BI and 2-CH3BI indicating its Through DFT quantum-chemical calculations a correlation be-
lowest donor ability. According to these theoretical results and tween parameters related to the electronic structure of benzimid-
the experimentally found inhibition efficiencies, it can be affirmed azole and two of its derivatives and their potential to inhibit the
that 2-SHBI has more potency to get adsorbed on the mild steel corrosion process could be established. Most of the calculated
surface than BI and 2-CH3BI. molecular parameters in the neutral form of the inhibitors calcu-
The ionization potential (I) and the electron affinity (A) can be lated by B3LYP/6-311G++ (d,p) level show excellent correlation
calculated by application of the Koopmans’ theorem [35]. This the- with inhibition efficiency of the inhibitors studied, confirming
orem establishes a relation between the energies of the HOMO and the reliability of the method employed. From the theoretical data
the LUMO and the ionization potential and the electron affinity, the inhibitive effectiveness order for the studied compounds is 2-
respectively. Although there exist no formal proof of this theorem SHBI > 2-CH3BI > BI and this agrees well with experiment.
660 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 657–660

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