Theoretical investigation of heterocyclic

compounds on corrosion inhibition

behavior of copper in hydrochloric acid
medium
S. Issaadi *, T. Douadi
Department of Engineering Process, Faculty of
Technology, University of Setif-1, DZ-19000,
Setif-Algeria.
issaadi2001@yahoo.fr
Abstract
Quantum chemical calculations based on DFT
method were performed on two schiff bases
compounds, used as corrosion inhibitors for
copper in HCl media to determine the
relationship between the molecular structure of
schiff base and inhibition efficiency. Quantum
chemical parameters such as the highest
occupied molecular orbital energy (EHOMO), the
lowest unoccupied molecular orbital energy
(ELUMO), energy gap (E), dipole moment (l),
electronegativity (v), electron affinity (A), global
ionization potential (I), the fraction of electrons
transferred (N), and the total energy (TE), were
calculated. The theoretically obtained results
were found to be consistent with the
experimental data reported.
Keywords:
chemical

Optimization,

DFT,

Quantum

acts as an electrophile; and the nucleophile

centers of inhibitor molecule are normally
heteroatoms with free electron pairs that are
readily available for sharing, to form a bond.
Organic compounds, containing functional
electronegative groups and p-electron in triple
or conjugated double bonds, are usually good
inhibitors. Heteroatoms, such as sulfur,
phosphorus, nitrogen and oxygen, together
with aromatic rings in their structure are the
major adsorption centers. The planarity and the
lonely electron pairs in the heteroatoms are
important features that determine the
adsorption of these molecules on the metallic
surface. The structural parameters, such as the
frontier molecular orbital energy HOMO
(highest occupied molecular orbital) and
LUMO (lowest unoccupied molecular orbital),
the charge distribution of the studied
inhibitors, the absolute electronegativity (v)
values, and the fraction of electrons (N)
transfer from inhibitors to iron were calculated
and correlated with inhibition efficiencies.
II.

I. INTRODUCTION
The use of corrosion inhibitor is one of the
most effective measures for protecting metal
surfaces
against
corrosion
in
acid
environments [1]. Some organic compounds
are found to be effective corrosion inhibitors
for many metals and alloys. Generally,
inhibitor molecules may physically or
chemically adsorb on a corroding metal
surface. In any case, adsorption is generally
over the metal surface forming an adsorption
layer that functions as a barrier protecting the
metal from the corrosion [2, 3]. It has been
commonly recognized that an organic inhibitor
usually promotes formation of a chelate on a
metal surface, by transferring electrons from
the organic compounds to the metal and
forming a coordinate covalent bond during the
chemical adsorption. In this way, the metal

THEORY AND COMPUTATIONAL DETAILS

DFT (density functional theory) methods were

used in this study. These methods have
become very popular in recent years because
they can reach exactitude similar to other
methods in less time and less expensive from
the computational point of view. In agreement
with the DFT 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 function for
calculating the energy constitutes the
fundamental base of DFT [4]. All the
calculations were done by GAUSSIAN 03 W
software , using the B3LYP functional and a 631G basis set. The B3LYP, a version of DFT
method.

II. a. Quantum chemical calculation

organic molecule (L)
Quantum chemical calculations were carried
out to find a relationship between the
molecular structure of the synthesized inhibitor
and its inhibition effect. In the present work,
the structure parameters and adsorptive
performance of the synthesized inhibitor are
used to elucidate the inhibition mechanism.
The corresponding molecule geometries were
optimized and then, the energies were
calculated at B3LYP/6-31G (d, p) level. The
optimized geometry and the frontier molecule
orbital density distributions of the molecule are
shown in Fig. 1 and the quantum chemical
parameters of the optimized molecular and
protonated (HL) structures of the L inhibitor
are listed in Table 1. It has been found that the
HOMO is located in the region around the
nitrogen and oxygen atoms. This probably
indicates that the preferred active sites for an
electronic attack and the favorite sites to
interact with the metal surface are located
within the region around the nitrogen and
oxygen atoms. For the HOMO of molecule, the
two nitrogen atoms (N47 and N48) of
azomethine groups, also the two oxygen atoms
(O33 and O41) of furan heterocyclic ring are
observed to have electron densities with
Mulliken atomic charges of (-0.47), (-0.47), (0.43) and (-0.43), respectively. Subsequently,
molecule is able to adsorb on the copper
surface by donating the unshared pair of
electrons from N and O atoms to the vacant dorbitals of copper, and thus prevent copper to
be corroded. The calculated quantum chemical
data include the energy of the fully occupied
molecular orbital (EHOMO = -5.53 eV), energy
of the lowest unoccupied molecular orbital
(ELUMO = -1.53 eV), dipole moment ( = 3.03
D), the energy gap, E (ELUMO -EHOMO = 4.00
eV). The high value of EHOMO (-5.53 eV) is
likely to indicate a tendency of the molecule to
donate electrons to the appropriate acceptor
molecule with low energy and empty
molecular orbital, whereas the value of ELUMO
(-1.53 eV) indicates the ability of the molecule
to accept electrons. Therefore, the value of E
provides a measure for the stability of the
formed complex on the metal surface. From
Mulliken charge analysis (Fig. 1), it is obvious
that nitrogen and oxygen atoms of the L
inhibitor hold negative charges. Thus, the
adsorption of L on the metal surface can occur
directly involving the displacement of
molecules with water from the metal surface.
The high inhibition efficiency of a molecule
can be attributed to the high value of dipole

moment and to the low value of E. The

results of the high dipole moment and the low
energy gap indicate that electron transfer from
molecule to the surface takes place during
adsorption on the copper surface [5].
The transferred electrons number (N) was
also calculated depending on the quantum
chemical method [6].

Cu inh
2 Cu inh

(1)

Where Cu and inh denote the absolute

electronegativity of copper and the inhibitor
molecule, respectively; Cu and inh are the
absolute hardness of copper and the inhibitor
molecule, respectively. These quantities are
related to the electron affinity (A) and
ionization potential (I)

A
2

I A
2

I and A are related in turn to EHOMO and ELUMO

I = -EHOMO
A = -ELUMO
The values of and were calculated by using
the values of I and A obtained from quantum
chemical calculation. Using theoretical values
of Cu = 4.48 eV/mol and of Cu = 0 eV/mol
for
copper
according
to
Pearsons
electronegativity scale assuming that for a
metallic bulk I = A, because they are softer
than neutral metallic atoms [7].
N, which is the fraction of electrons
transferred from inhibitor to the copper
surface, was calculated (Table 1). Values of
N showed inhibition effect resulted from
electrons donation. According to Lukovits [8],
if N <3.6, the inhibition efficiency increased
with increasing electron donating ability at the
metal surface. In this study, SB was the donor
of electrons, and the copper surface was the
acceptor.
II. b. Quantum chemical results of the
protonated organic molecule (HL)
Electrochemical reactions take place in an
aqueous medium in which the compound with
atoms having lone pair of electrons is
protonated. The protonated species have been
reported to also take part in adsorption on the
metal surface. Therefore, it is interesting to
study the molecular properties of the
protonated species and compare them with
those of the neutral species to determine the
ideal ones to bind to the metal surface. The
protonated species are shown in Fig. 2 and
their molecular properties are reported in Table

1. Since the EHOMO is higher for the neutral

species than for the protonated species, this
indicates that the neutral species has a greater
tendency to donate electrons and therefore, to
bind to the metal surface. The E values
suggest that the neutral species is also more
reactive than the protonated species. It is
therefore reasonable to infer that the
protonated species of molecule are less likely
to interact with metal surface as compared to
the neutral species. This confirms the
experimental evidence that both physisorption
and chemisorption mechanisms are involved in
the adsorption process of molecule on copper
surface.

Table 1. Calculated quantum chemical parameters for

molecular and protonated structure

DFT parameter

L(neutral)

EHOMO (eV)
ELUMO (eV)
E
(D)
N (e)

-5.53
-1.53
4.00
3.03
0.23

III.

CONCLUSION

HL
(protonated)
-5.10
0.15
5.25
1.00
0.37

The relationships between inhibition efficiency

of copper in 1 M HCl and the EHOMO, ELUMOEHOMO, and N of L were calculated by DFT
method. The inhibition efficiency increased
with the increase in EHOMO and decrease in
ELUMO - EHOMO. HL had the highest inhibition
efficiency because it had the highest HOMO
energy and N values, and it was most capable
of offering electrons.

References

Fig. 1. Frontier molecule orbital density distributions using

DFT at the B3LYP/6-31G (d,p). Top: HOMO, bottom:
LUMO

Fig. 2. Frontier molecule orbital density distributions of

protonated structure (HL) using DFT at the B3LYP/6-31G
(d,p). Top: HOMO, bottom: LUMO

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