Int. J. Electrochem. Sci.

, 7 (2012) 6353 - 6364

International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org


A Theoretical Investigation on the Corrosion Inhibition of
Copper by Quinoxaline Derivatives in Nitric Acid Solution

A.Zarrouk
1,*
, H. Zarrok
2
, R. Salghi
3
, B. Hammouti
1
, S.S. Al-Deyab
6
, R. Touzani
1, 4
, M. Bouachrine
5
,
I. Warad
6
, T. B. Hadda
7

1
LCAE-URAC18, Facult des Sciences, Universit Mohammed 1
er
, Oujda-60000, Morocco.
2
Laboratoire des Procdes de Sparation, Facult des Sciences, Universit Ibn Tofail, Knitra,
Morocco.
3
Equipe de Gnie de lEnvironnement et Biotechnologie, ENSA, Universit Ibn Zohr, BP1136 Agadir,
Morocco.
4
Facult Pluridisciplinaire de Nador, Universit Mohammed Premier, BP 300, Selouane 62700, Nador,
Morocco.
5
UMIM, Facult Polydisciplinaire de Taza, Universit Sidi Mohamed Ben Abdellah, Taza, Morocco.
6
Petrochemical Research Chair, Chemistry Department, College of Science, King Saud University,
P.O. Box 2455, Riyadh 11451, Saudi Arabia
7
Laboratoire de Chimie des Matriaux, Facult des Sciences, Universit Mohammed Premier, Oujda-
60000, Morocco.
*
E-mail: azarrouk@gmail.com

Received: 28 May 2012 / Accepted: 11 June 2012 / Published: 1 July 2012


In the present work, a theoretical study of two quinoxaline-type organic compounds, (2Z)-2-[(3E)-3-
(2-oxo-2-phenylethylidene)-3, 4-dihydroquinoxalin-2(1H)-ylidene]-1 phenylethanone (Q5) and (Z)-2-
((E)-3-(2-oxo-2-phenylethylidene)-3, 4-dihydroquinoxalin-2(1H)-ylidene)-1-phenylethanone (Q6), has
been performed using density functional theory (DFT) at the B3LYP/6-31G(d) level in order to
elucidate the different inhibition efficiencies and reactive sites of these compounds as corrosion
inhibitors. The efficiencies of corrosion inhibitors and the global chemical reactivity relate to some
parameters, such as highest occupied molecular orbital energy (E
HOMO
), lowest unoccupied molecular
orbital energy (E
LUMO
), energy gap (E), dipole moment () , electronegativity (), electron affinity
(A), global hardness (), softness (), ionization potential (I), the fraction of electrons transferred (N),
the global electrophilicity () and the total energy (TE), were calculated. All calculation has been
performed by considering Density Functional Theory (DFT) using the GAUSSIAN03W suite of
programs. The calculated results are in agreement with the experimental data on the whole.


Keywords: Quinoxalines, Nitric acid, Copper, Corrosion inhibitors, Density Functional Theory (DFT).


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6354
1. INTRODUCTION
Copper and copper alloys are extensively used in various industry applications, both in aqueous
and non-aqueous environments. Copper has found considerable use in the electrotechnical industry due
to its high electrical conductivity. The conductivity is, next to the conductivity of silver, the highest
electrical conductivity at room temperature of all metals [1]. This high value is due to the mall energy
difference between the valence and conduction band allowing electrons to flow freely. Copper does not
displace hydrogen from acid solutions and it is therefore unattacked in non-oxidising acid
environments. Nevertheless, most acidic solutions contain dissolved air that enables some corrosion to
take place. Many organic molecules are used to inhibit copper corrosion [26]. The primary step in the
action of organic corrosion inhibitors in acid solutions is usually adsorption at the metalsolution
interface. The adsorption process depends on the electronic characteristic of the molecules (adsorbate),
the chemical composition of the solution, nature of the metal surface, temperature of the reaction and
on the electrochemical potential at the metal solution interface [7]. The adsorption requires the
existence of attractive forces between the adsorbate and the metal. According to the type of forces,
adsorption can be physisorption or chemisorption or a combination of both [8]. Physisorption is due to
electrostatic attractive forces between inhibiting organic ions or dipoles and the electrically charged
surface of the metal. Chemisorption is due to interaction between unshared electron pairs or electrons
with the metal in order to form a coordinate type of bond. The adsorption occurs from active centers
such as P, Se, S, N and O atoms, the double or triple bonds and also aromatic rings. The effect of the
molecular structure on the chemical reactivity has been subject of great interest in several disciplines
of chemistry. The quantum chemical calculations have been widely used to study the reaction
mechanisms and to interpret the experimental results as well as to solve chemical ambiguities. This is a
useful approach to investigate the mechanisms of reaction in the molecule and its electronic structure
level and electronic parameters can be obtained by means of theoretical calculations using the
computational methodologies of quantum chemistry [9]. The advancement in methodology and
implementations has reached a point where predicted properties of reasonable accuracy can be
obtained from density functional theory (DFT) calculations [10]. The geometry of the inhibitor in its
ground state, as well as the nature of their molecular orbitals, highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO) are involved in the properties of activity
of inhibitors. The inhibition property of a compound has been often correlated with energy of HOMO,
LUMO and HOMOLUMO gap. The inhibition efficiency of the two inhibitors was studied previously
[11].
The objective of this paper is to investigate the dependence of inhibition efficiency of these
compounds on theoretical chemical parameters such as the energies of highest occupied molecular
orbital (E
HOMO
) and the lowest unoccupied molecular orbital (E
LUMO
), the energy difference (E)
between E
HOMO
and E
LUMO
, dipole moment (), electronegativity (), electron affinity (A), global
hardness (), softness (), ionization potential (I), the global electrophilicity (), the fraction of
electrons transferred (N) and the total energy (TE). The chemical structures of the compounds studied
are given in Fig 1.

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6355
N
N
O
O
H
H

N
N
O
O
H
H

(Q5)

(2Z)-2-[(3E)-3-(2-oxo-2-phenylethylidene)-
3,4-dihydroquinoxalin-2(1H)-ylidene]-1-
phenylethanone
(Q6)

(Z)-2-((E)-3-(2-oxo-2-phenylethylidene)-3,4-
dihydroquinoxalin-2(1H)-ylidene)-1-
phenylethanone

Figure 1. The molecular structures of the investigated inhibitors Q5 and Q6.



2. QUANTUM CHEMICAL CALCULATIONS
Complete geometrical optimizations of the investigated molecules are performed using DFT
(density functional theory) with the Becks three parameter exchange functional along with the Lee
YangParr nonlocal correlation functional (B3LYP) [1214] with 6- 31G* basis set is implemented in
Gaussian 03 program package [15]. This approach is shown to yield favorable geometries for a wide
variety of systems. This basis set gives good geometry optimizations. The geometry structure was
optimized under no constraint. The following quantum chemical parameters were calculated from the
obtained optimized structure: The highest occupied molecular orbital (E
HOMO
) and the lowest
unoccupied molecular orbital (E
LUMO
), the energy difference (E) between E
HOMO
and E
LUMO
, dipole
moment (), electronegativity (), electron affinity (A), global hardness (), softness (), ionization
potential (I), the global electrophilicity (), the fraction of electrons transferred (N) and the total
energy (TE).



3. RESULTS AND DISCUSSION
The inhibition of copper using substituted quinoxalines as corrosion inhibitors were
investigated experimentally. Table 1 indicates clearly a decrease in the corrosion rate in the presence of
Q5 and Q6. This effect is hugely marked at higher concentration of inhibitors. The inhibitive action is
more explicit by E
I
% data which increases with inhibitor concentration to reach 82.9% for Q5, 71.9%
for Q6. Quantum chemical calculations have been widely used to study reaction mechanisms. They
have also proved to be a very powerful tool for studying corrosion inhibition mechanisms [16].
Recently, theoretical prediction of the efficiency of corrosion inhibitors has become very popular in
parallel with the progress in computational hardware and the development of efficient algorithms
which assisted the routine development of molecular quantum mechanical calculations [17]. All
quantum chemical properties were obtained after geometric optimization with respect to the all nuclear
Int. J. Electrochem. Sci., Vol. 7, 2012

6356
coordinates using KohnSham approach at DFT level. The optimized structure of the studied
compound as shown in Fig. 2.

Table 1. Summarized the inhibition efficiency (E
I
%) obtained by addition of Q5 and Q6 at different
concentrations on the corrosion of copper in 2M HNO
3
solution determined by
potentiodynamic polarization [11].

Conc (M) E
corr

(mV/SCE)
-b
c
(mV/dec)
I
corr
(A/cm
2
)
EI (%)
HNO
3
2 34.0 304 365.1 -
10
-3
-04.2 182 062.2 82.9
Q5 10
-4
11.8 185 126.2 65.4
10
-5
14.6 167 291.8 20.1
10
-6
15.9 179 328.5 10.0
10
-3
20.1 190 102.5 71.9
Q6 10
-4
20.5 190 153.8 57.9
10
-5
25.9 205 290.7 20.4
10
-6
264 193 315.1 13.7




Q5 Q6

Figure 2. Optimized structure of studied molecules obtained by B3LYP/6-31G* level.

The frontier orbital (highest occupied molecular orbital HOMO and lowest unoccupied
molecular orbital LUMO) of a chemical species are very important in defining its reactivity. Fukui first
recognized this. A good correlation has been found between the speeds of corrosion and E
HOMO
that is
often associated with the electrondonating ability of the molecule. Survey of literature shows that the
adsorption of the inhibitor on the metal surface can occur on the basis of donoracceptor interactions
between the -electrons of the heterocyclic compound and the vacant d-orbital of the metal surface
atoms [18], high value of E
HOMO
of the molecules shows its tendency to donate electrons to appropriate
acceptor molecules with low energy empty molecular orbitals. Increasing values of E
HOMO
facilitate
adsorption and therefore enhance the inhibition efficiency, by influencing the transport process through
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6357
the adsorbed layer. Similar relations were found between the rates of corrosion and E
(E = E
LUMO
E
HOMO
) [1921]. The energy of the lowest unoccupied molecular orbital indicates the
ability of the molecule to accept electrons. The lower the value of E
LUMO
, the more probable the
molecule would accept electrons. Consequently, concerning the value of the energy gap E, larger
values of the energy difference will provide low reactivity to a chemical species. Lower values of the
E will render good inhibition efficiency, because the energy required to remove an electron from the
lowest occupied orbital will be low [22]. Another method to correlate inhibition efficiency with
parameters of molecular structure is to calculate the fraction of electrons transferred from inhibitor to
metal surface. According to Koopmans theorem [23], E
HOMO
and E
LUMO
of the inhibitor molecule are
related to the ionization potential (I) and the electron affinity (A), respectively. The ionization potential
and the electron affinity are defined as I = - E
HOMO
and A = - E
LUMO
, respectively. Then absolute
electronegativity () and global hardness () of the inhibitor molecule are approximated as follows
[22]:

2
I A
_
+
=
(1)

2
I A
q

=
(2)

The global electrophilicity index was introduced by Parr [24] and is given by:

2
2

e
q
= (3)

Thus the fraction of electrons transferred from the inhibitor to metallic surface, N, is given by
[25]:

( ) 2
Cu inh
Cu inh
N
_ _
q q

A =
+
(4)

In order to calculate the fraction of electrons transferred, a theoretical value for the
electronegativity of bulk copper was used
Cu
= 4.48 eV/mol [23], and a global hardness of ,
Cu
= 0
eV/mol by assuming that for a metallic bulk I = A [26] because they are softer than the neutral metallic
atoms.
Quantum chemical parameters obtained from the calculations which are responsible for the
inhibition efficiency of inhibitors, such as the highest occupied molecular orbital (E
HOMO
), energy of
lowest unoccupied molecular orbital (E
LUMO
), HOMOLUMO energy gap (E
H-L
), dipole moment ()
and total energy (TE), electronegativity (), electron affinity (A), global hardness (), softness (),
ionization potential (I), The global electrophilicity (), the fraction of electrons transferred from the
inhibitor to iron surface (N) and the total energy (TE) , are collected in Table 2.

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6358
Table 2. Calculated quantum chemical parameters of the studied compounds.

Quantum parameters Q5 Q6
HOMO
E
(eV)
-5.4378 -5.540
LUMO
E
(eV)
-2.17812 -1.964
E A
gap (eV)
3.259 3.576

(debye)
8.1609 9.6768
EI (%) 82.9 71.9
HOMO
I E =
(eV)
5.4378 5.540

LUMO
A E =
(eV)
2.17812 1.964
2
A I +
= _
(eV)
3.80796 3.752
2
A I
= q
(eV)
1.62984 1.788
q
o
1
=

0.61356 0.55928
2
2

e
q
=

20.43154 26.18581
( ) 2
Cu inh
Cu inh
N
_ _
q q

A =
+

0.54766 0.65083
TE (eV) -1185.3283101 -1188.9302589

In Fig. 3, we have presented the frontier molecule orbital density distributions of the studied
compounds: HOMO (right); LUMO (left). Analysis of Fig. 3 shows that the distribution of two
energies HOMO and LUMO, we can see that the electron density of the HOMO location in the
Quinoxaline molecules is mostly distributed near the nitrogen (NH) and oxygen (= O) atoms and
quinoxaline ring indicating that these are the favorite sites for adsorption, while the density LUMO
was distributed almost of the entire molecules.

HOMO LUMO






Q5

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6359





Q6




Figure 3. Schematic representation of HOMO and LUMO molecular orbital of studied molecules.

According to the frontier molecular orbital theory (FMO) of chemical reactivity, transition of
electron is due to interaction between highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) of reacting species [27]. E
HOMO
is a quantum chemical
parameter which is often associated with the electron donating ability of the molecule. High value of
E
HOMO
is likely to a tendency of the molecule to donate electrons to appropriate acceptor molecule of
low empty molecular orbital energy [28]. The inhibitor does not only donate electron to the
unoccupied d orbital of the metal ion but can also accept electron from the d-orbital of the metal
leading to the formation of a feed back bond. The highest value of E
HOMO
-5.4378 (eV) of Q5 indicates
the better inhibition efficiency.
It has also been found that an inhibitor does not only donate an electron to the unoccupied d
orbital of the metal ion but can also accept electrons from the d orbital of the metal leading to the
formation of a feedback bond. Therefore, the tendency for the formation of a feedback bond would
depend on the value of E
LUMO
. The lower the E
LUMO
, the easier is the acceptance of electrons from the
d orbital of the metal [21]. Based on the values of E
LUMO
, the order obtained for the decrease in
inhibition efficiency (Q5 > Q6) was also similar to the one obtained from experimental results.
The separation energy, E = E
LUMO
- E
HOMO
is an important parameter as a function of
reactivity of the inhibitor molecule towards the adsorption on metallic surface. As E decreases, the
reactivity of the molecule increases leading to increase the inhibition efficiency of the molecule. The
results obtained from quantum chemical calculation are listed in Table 2. The calculations indicate that
Q5 has the lowest value which means the highest reactivity among the other inhibitor and accordingly
the highest inhibition efficiency which agrees well with the experimental observations. The order of
reactivity in this case will be:
Q5 > Q6.
Absolute hardness and softness are important properties to measure the molecular stability and
reactivity. It is apparent that the chemical hardness fundamentally signifies the resistance towards the
deformation or polarization of the electron cloud of the atoms, ions or molecules under small
perturbation of chemical reaction. A hard molecule has a large energy gap and a soft molecule has a
small energy gap [29]. In our present study Q5 with low hardness value 1.62984 (eV) compared with
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6360
other compound have a low energy gap. Normally, the inhibitor with the least value of global hardness
(hence the highest value of global softness) is expected to have the highest inhibition efficiency [30].
For the simplest transfer of electron, adsorption could occur at the part of the molecule where softness
(), which is a local property, has a highest value [19]. Q5 with the softness value of 0.61356 has the
highest inhibition efficiency.
The most widely used quantity to describe the polarity is the dipole moment of the molecule
[31]. Dipole moment is the measure of polarity of a polar covalent bond. It is defined as the product of
charge on the atoms and the distance between the two bonded atoms. The total dipole moment,
however, reflects only the global polarity of a molecule. For a complete molecule the total molecular
dipole moment may be approximated as the vector sum of individual bond dipole moments. The dipole
moment ( in Debye) is another important electronic parameter that results from non uniform
distribution of charges on the various atoms in the molecule. The high value of dipole moment
probably increases the adsorption between chemical compound and metal surface [32]. The energy of
the deformability increases with the increase in , making the molecule easier to adsorb at the Cu
surface. The volume of the inhibitor molecules also increases with the increase of . This increases the
contact area between the molecule and surface of copper and increasing the corrosion inhibition ability
of inhibitors. In our study, there is no direct relationship between the E
I
(%) and the dipole moment.
In literature it has been reported that the values of N show inhibition effect resulted from
electrons donation [23, 33]. According to Lukovitss study [33], if the value of N < 3.6, the inhibition
efficiency increased with increasing electron donating ability of inhibitor at the metal surface. Also it
was observed [34] that inhibition efficiency increased with increase in the values of N. However, our
study reveals that there is no regular trend in the inhibition efficiency by increasing values of N.
The total energy calculated by quantum chemical methods is also a beneficial parameter. The
total energy of a system is composed of the internal, potential, and kinetic energy. Hohenberg and
Kohn [35] proved that the total energy of a system including that of the many body effects of electrons
(exchange and correlation) in the presence of static external potential (for example, the atomic nuclei)
is a unique functional of the charge density. The minimum value of the total energy functional is the
ground state energy of the system. The electronic charge density which yields this minimum is then the
exact single particle ground state energy. In our study the total energy of the best inhibitor Q5 is equal
to -1185.3283101 eV, this value is lower than that of the compound Q6.

Analysis of charge repartition of compounds Q5 and Q6
The comparison of the reparation atomic charge (Fig. 4) of Q5 and Q6 shows no evident and
apparent difference but the look for lowest energy conformer of Q5 and Q6 lead us to conformers1
which have respective energy of 97.02 and 92.38 Kcal/mol (Fig. 5).

Crystalline structure analysis of compound Q5
The crystalline structure of Q5 (Fig. 6) is fully in agreement with the structures proposed for
conformer 1 with lowest energy. The molecule is quasi-planar [36] with a C symmetry axis: the
external phenyl rings are twisted by 25 .
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6361



Q5 Q6


Q5 Q6

Figure 4. Charge repartition of quinoxalines Q5 and Q6.




Q5 (Conf-1)
Energy: 97.02 Kcal/mol
Q5 (Conf-2)
Energy: 125.88 Kcal/mol
Q5 (Conf-3)
Energy: 152.69 Kcal/mol
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6362



Q6 (Conf-1)
Energy: 92.38 Kcal/mol
Q6 (Conf-2)
Energy: 93.8 Kcal/mol
Q6 (Conf-3)
Energy : 93.97 Kcal/mol

Figure 5. Lowest and highest energy conformers of quinoxalines Q5 and Q6.

The nitrogen atom N(1) is trivalent with an N(1)-H(1) bond length of about 0.88 A, confirming
the position of the acidic proton. In addition, N(1), C(2), C(8a) and H(1) are perfectly coplanar,
resulting from the sp2 hybridization of the nitrogen atom due to the conjugation with the delocalized
pi-system. The C(9)-C(10) and C(2)-C(3) distances [1.431(2) and 1.482(3) A, respectively] lie in
between single and double bond lengths, confirming the high electronic delocalization. The H(1) ---
O(1) distance of about 1.8 A. and the N(1), H(1), O(1) angle of ca. 15, suggests an intra-molecular
N(1)-H(1) --- O(1) hydrogen bond in accordance with the strong NMR deshielding of H(1) [15.0
ppm].[37]



Figure 6. ORTEP drawing of compound Q5.

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6363
4. CONCLUSION
The correlation between the quantum chemical parameters and inhibition efficiency of some
quinoxaline compounds was investigated using DFT/B3LYP calculations. The inhibition efficiency of
the inhibitor are closely related to the quantum chemical parameters, the highest occupied molecular
orbital (E
HOMO
), energy of lowest unoccupied molecular orbital (E
LUMO
), HOMOLUMO energy gap
(E
H-L
), the hardness (), the softness () and the fraction of electrons transferred (N) for the neutral
inhibitors and no significant relationship was found with parameters, dipole moment () and the total
energy (TE).


ACKNOWLEDGEMENTS
Prof. S.S. Al-Deyab and Prof B. Hammouti extend their appreciation to Deanship of Scientific
Research at King Saud University for funding the work through the research group project 089.


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