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Advances in Materials Science and Engineering

Volume 2015, Article ID 519606, 5 pages
http://dx.doi.org/10.1155/2015/519606

Research Article
Quantum Chemical Study on the Corrosion Inhibition of
Some Oxadiazoles

Hong Ju, Li Ding, Can Sun, and Jie-jing Chen

College of Mechanical and Electronic Engineering, China University of Petroleum, Qingdao 266580, China

Correspondence should be addressed to Hong Ju; juhong@upc.edu.cn

Received 10 August 2014; Accepted 9 September 2014

Academic Editor: Antonio Riveiro

Copyright © 2015 Hong Ju et al. This is an open access article distributed under the Creative Commons Attribution License, which
permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Quantum chemical calculations based on DFT method were performed on three nitrogen-bearing heterocyclic compounds used as
corrosion inhibitors for the mild steel in acid media to determine the relationship between the molecular structure of inhibitors and
inhibition efficiency. The structural parameters, such as energy and distribution of highest occupied molecular orbital (HOMO) and
lowest unoccupied molecular orbital (LUMO), the charge distribution of the studied inhibitors, the absolute electronegativity (𝜒)
values, and the fraction of electrons (Δ𝑁) transfer from inhibitors to mild steel were also calculated and correlated with inhibition
efficiencies. The results showed that the inhibition efficiency of inhibitors increased with the increase in energy of HOMO and
decrease in energy gap of frontier molecular orbital, and the areas containing N and O atoms are most possible sites for bonding
the steel surface by donating electrons to the mild steel.

1. Introduction have at least two factors within their structures, which is

the reason of their effective inhibiting. The planarity (_) and
Acid solutions are widely used in industry, for example, the lonely electron pairs in the heteroatoms are important
chemical cleaning, descaling, and pickling, which leads to features that determine the adsorption of these molecules on
corrosive attack. Therefore, the consumption of inhibitors the metallic surface by transferring electrons from the organic
to reduce corrosion has increased in recent years [1–4]. The compounds to the metal and forming a coordinate covalent
majority of the well-known inhibitors are organic compounds bond during the chemical adsorption [6, 7].
containing heteroatoms, such as oxygen, nitrogen, or sulphur, Theoretical chemistry has been used recently to explain
and multiple bonds, which allow an adsorption on the metal the mechanism of corrosion inhibition, such as quantum
surface [2, 3]. In any case, adsorption is generally over the chemical calculations [10–13]. Quantum chemical calcula-
metal surface forming an adsorption layer that functions as a tions have been proved to be a very powerful tool for
barrier protecting the metal from the corrosion [2, 3]. studying the mechanism [14–16]. The objective of this work
In order to evaluate compounds as corrosion inhibitors is to present a theoretical study on electronic and molecular
and to design novel inhibitors, much more research works structures of three heterocyclic compounds (Figure 1) and
were concentrated on the studies of the relationship between to determine relationship between molecular structure of
structural characteristics of the organic compounds and the compounds and inhibition efficiency. The structural
their inhibiting effects [5–8]. It had been suggested that parameters, such as energy and distribution of highest
the most effective factors for the inhibiting effects are the occupied molecular orbital (HOMO) and lowest unoccupied
electronegative atoms (such as, N, S, P, and O) [5, 6], the molecular orbital (LUMO), the charge distribution of the
unsaturated bonds (such as double bonds or triple bonds) studied inhibitors, the absolute electronegativity (𝜒) values,
[7, 8], and the plane conjugated systems including all kinds and the fraction of electrons (Δ𝑁) transfer from inhibitors to
of aromatic cycles, of which they can offer special active mild steel were also calculated and correlated with inhibition
electrons or vacant orbital to donate or accept electrons. efficiencies. This work has great significance for the investiga-
Heterocyclic compounds, kind of effective inhibitors [6–9], tion of inhibition mechanism in theory. And it will be helpful
2 Advances in Materials Science and Engineering

O O N O N
N N N N
N–N N–N N–N
2-POX 3-POX 4-POX

Figure 1: The chemical structure of the investigated compounds.

to provide reference for screening corrosion inhibitors before 86

3-POX
the experiment.
81
2-POX

IE (%)
2. Theory and Computational Details 76

71
Density functional theory (DFT) methods were used in this
study. These methods have become very popular in recent 4-POX
66
years because they can reach exactitude similar to other −7.4 −7.35 −7.3 −7.25 −7.2 −7.15 −7.1 −7.05
methods in less time and they are less expensive from the EHOMO (eV)
computational point of view. In agreement with the DFT
Figure 2: The relations between corrosion IE and 𝐸HOMO of 𝑛-POX.
results, energy of the fundamental state of a polyelectronic
system can be expressed through the total electronic density,
and, in fact, the use of electronic density instead of wave 86
function for calculating the energy constitutes the funda- 3-POX
mental base of DFT [16]. All the calculations were done by 81
2-POX
GAUSSIAN 03W software [17], using the B3LYP functional
IE (%)

76
[18, 19] and a 6-31G∗ basis set [19]. The B3LYP, a version of
DFT method, uses Beche’s three-parameter functional (B3) 71
and includes a mixture of HF with DFT exchange terms 4-POX
associated with the gradient corrected correlation functional 66
of Lee, Yang, and Parr (LYP) [18, 19]. This approach is shown −2.63 −2.58 −2.53 −2.48
to yield favorable geometries for a wide variety of systems. ELUMO (eV)
This basis set gives good geometry optimizations.
Figure 3: The relations between corrosion IE and 𝐸LUMO of 𝑛-POX.

3. Results
nitrogen and oxygen atoms charged a large electron density
Table 1 presents the calculated parameters for the three and might form adsorption active centers.
selected compounds. The measured average inhibition effi-
ciencies (%) of these three heterocyclic compounds were also
listed in the table [20]. 4. Discussion
The relationship between corrosion inhibition efficiency 4.1. Correlation between MO Energy Level and Inhibition
and HOMO energy levels for these three compounds is Efficiency. Frontier orbital theory is useful in predicting
plotted in Figure 2. As clearly seen in the figure, the inhibition adsorption centers of the inhibitor molecules responsible for
efficiency increased with the 𝐸HOMO level rising. In Figure 3, the interaction with surface metal atoms [5, 15]. Terms involv-
inhibition efficiency is plotted against the LUMO energy, ing the frontier MO could provide dominative contribution,
showing that the inhibition efficiency reduced with the because of the inverse dependence of stabilization energy
𝐸LUMO level increase. The relationship between the inhibition on orbital energy difference [5]. Moreover, the gap between
efficiency and the energy gap (𝐸LUMO − 𝐸HOMO ) is negative the HOMO and LUMO energy levels of the molecules was
(Figure 4). another important factor that should be considered. Report-
The frontier molecule orbital density distributions of edly, excellent corrosion inhibitors are usually those organic
three 𝑛-POXs were presented in Figure 5. As seen from compounds which not only offer electrons to unoccupied
the figure, the distributions of HOMO and LUMO were orbital of the metal, but also accept free electrons from the
mainly average around the whole compound structure, but metal [5, 11].
the population densities of three compounds’ frontier orbitals According to Gece and Bilgiç [20], when the position of
have a more obvious difference. 2-POX and 3-POX have N atoms was changing, the corrosion inhibition efficiency
higher and more uniform population densities than 4-POX. changed. The quantum chemistry calculation in this study
The Mulliken charge populations of the three 𝑛-POXs revealed that the HOMO energy level of 3-POX was boosted
were also calculated (Figure 6). It can be seen that the area of significantly while the energy gap dropped sharply. The linear
Advances in Materials Science and Engineering 3

Table 1: Molecular property of 𝑛-POXs calculated with B3LYP/6-31G∗ .

𝐸HOMO 𝐸LUMO (𝐸LUMO − 𝐸HOMO ) Dipole moment Inhibition efficiency

Compound
[eV] [eV] [eV] (Deby) 𝜂 (%)
2-POX −7.33 −2.53 4.80 0.431 79
3-POX −7.15 −2.58 4.57 0.466 84
4-POX −7.37 −2.48 4.89 0.423 68

86 a theoretical 𝜒 value of 7 eV/mol and 𝜂 value of 0 eV/mol for

3-POX iron atom [21], Δ𝑁, the fraction of electrons transferred from
81 inhibitor to the iron molecule, was calculated. And the plot
2-POX
of inhibition efficiency versus Δ𝑁 (Figure 7) clearly shows
IE (%)

76 that the inhibition efficiency increased with the Δ𝑁 increase.

According to other reports [21, 22], values of Δ𝑁 showed that
71
inhibition effect resulted from electrons donation. Agreeing
4-POX with Lukovits’s study [22], if Δ𝑁 < 3.6, the inhibition
66
4.55 4.6 4.65 4.7 4.75 4.8 4.85 4.9 efficiency increased with increasing electron-donating ability
ELUMO − EHOMO (eV) at the metal surface. In this study, the three 𝑛-POXs were the
donators of electrons, and the iron surface was the acceptor.
Figure 4: The relations between corrosion IE and HOMO-LUMO The compounds were bound to the metal surface and thus
energy gaps of 𝑛-POX. formed inhibition adsorption layer against corrosion. 2-
POX had the highest inhibition efficiency because it had
the highest HOMO energy and Δ𝑁 values, and it had the
correlation between MO energy level and the corrosion greatest ability of offering electrons, and 2-POX had the
inhibition efficiency of the 𝑛-POXs (Figures 2, 3, and 4) lowest inhibition efficiency, for vice versa.
proved that the higher the HOMO energy of the inhibitor,
the greater the trend of offering electrons to unoccupied d 4.2. Correlation between Electronic Density and Inhibition Effi-
orbital of the metal and the higher the corrosion inhibition ciency. Frontier orbital energy level indicates the tendency
efficiency for iron in HCl acid solutions; in addition, the lower of bonding to the metal surface. Further study on formation
the LUMO energy, the easier the acceptance of electrons from of chelating centers in an inhibitor requires the information
metal surface, as the HOMO-LUMO energy gap decreased of spatial distribution of electronic density of the compound
and the efficiency of inhibitor improved. molecules [5].
The number of transferred electrons (Δ𝑁) was also The structure of the molecules can affect the adsorption
calculated depending on the quantum chemical method [21, by influencing the electron density at the functional group.
22]: Generally, electrophiles attack the molecules at negative
(𝜒Fe − 𝜒inh ) charged sites. As seen from Figure 6, the electron density
Δ𝑁 = , (1) focused on N atoms. The regions of highest electron density
[2 (𝜂Fe + 𝜂inh )] are generally the sites which electrophiles attacked. So N and
where 𝜒Fe and 𝜒inh denote the absolute electronegativity O atoms were the active center, which had the strongest ability
of iron and the inhibitor molecule, respectively; 𝜂Fe and of bonding to the metal surface. On the other side, HOMO
𝜂inh denote the absolute hardness of iron and the inhibitor (Figure 5) was mainly distributed on the areas containing
molecule, respectively. nitrogen and oxygen atoms. Thus, the areas containing N and
These quantities are related to electron affinity (𝐴) and O atoms were probably the primary sites of the bonding. And
ionization potential (𝐼): inhibition efficiency was enhanced by increase in HOMO
energy and electron density. It is concluded that the region of
(𝐼 + 𝐴) active centers transforming electrons from N atoms to iron
𝜒= , (2)
2 surface. The electron configuration of iron is [Ar] 4s2 3d6 ;
(𝐼 − 𝐴) the 3d orbitals are not fully filled with electrons. N and
𝜂= , (3) O atoms have lonely electron pairs that are important for
2
bonding unfilled 3d orbitals of iron atom and determining the
where 𝐼 and 𝐴 are related in turn to 𝐸HOMO and 𝐸LUMO : adsorption of the molecules on the metal surface. 3-POX had
the highest inhibition efficiency among the 𝑛-POX, which
𝐼 = −𝐸HOMO , (4)
resulted from the geometry change that led to HOMO energy
𝐼 = −𝐸HOMO . (5) increase and electron density distribution in the molecule.
On the contrary, 4-POX had the lowest inhibition efficiency
Values of 𝜒 and 𝜂 were calculated by using the values of 𝐼 because of the lowest and the most uneven population density
and 𝐴 obtained from quantum chemical calculation. Using of HOMO.
4 Advances in Materials Science and Engineering

2-POX 3-POX

4-POX

Figure 5: The frontier molecule orbital density distributions of three 𝑛-POXs: HOMO (left) and LUMO (right).

−0.496 0.496 −0.488 0.488 −0.479 0.479

2-POX 3-POX 4-POX

Figure 6: The Mulliken charge population of three 𝑛-POXs.

86 some sulphonamides by using density functional theory

3-POX (DFT) and some semiempirical methods. Their useful results
81 validated the accuracy of our calculations and results from
2-POX
IE (%)

76
their other analytic angles.

71 5. Conclusions
4-POX
66 The relationships between inhibition efficiency of iron in
0.42 0.43 0.44 0.45 0.46 0.47
perchloric acid solution and 𝐸HOMO , 𝐸HOMO −𝐸LUMO , and Δ𝑁
ΔN
of 𝑛-POXs were calculated by DFT method. The inhibition
Figure 7: The relations between corrosion IE and Δ𝑁 values of 𝑛- efficiency increased with the increase in 𝐸HOMO and decrease
POX. in 𝐸HOMO − 𝐸LUMO . 3-POX had the highest inhibition
efficiency because it had the highest HOMO energy and Δ𝑁
values, and it was most capable of offering electrons. The
distribution of electronic density shows that the molecules
Based on the discussion above, it can be concluded that of 𝑛-POXs had many negatively charged active centers. The
the 3-POX molecules have many active centers of negative electron density was found to be positively correlated with
charge. In addition, the areas containing N and O atoms are nitrogen and oxygen atoms, which resulted in increasing
the most possible sites of bonding metal surface by donating inhibition efficiency. The areas containing N and O atoms
electrons to the metal iron. According to these results, we are most possible sites for bonding the metal iron surface by
could calculate the quantum chemical parameters before the donating electrons to the metal.
experiment to forecast the inhibitor effectiveness. This can Quantum chemical calculations indicated that consid-
help improve accuracy and save time. ering only one parameter is not convenient; hence several
At present, more and more researchers are engaged in parameters or a composite index of more than two or more
the calculation of the quantum chemistry of the organic quantum chemical parameters were taken into consideration
heterocyclic inhibitors, especially the nitrogen-heterocyclic to characterize the inhibition activity of the molecules. Quan-
inhibitors. El Sayed et al. [23] proceed the quantum chem- tum chemical calculation approach is adequately sufficient to
ical calculation for corrosion inhibitions of some triazole, also forecast the inhibitor effectiveness using the theoretical
oxadiazole, and thiadiazole derivatives by using a Restricted approach. Moreover, it may be used to find the optimal group
Hartree-Fock (RHF) method. Arslan et al. [24] took the of parameters that might predict the structure and molecule
quantum chemical studies on the corrosion inhibition of suitability to be an inhibitor.
Advances in Materials Science and Engineering 5

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