Corrosion Science 52 (2010) 282–285

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

Short Communication

2,3-Diphenylbenzoquinoxaline: A new corrosion inhibitor for mild steel

in sulphuric acid
I.B. Obot a,*, N.O. Obi-Egbedi b
a
Department of Chemistry, Faculty of Science, University of Uyo, P.M.B 1017, Uyo, Akwa Ibom State, 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: 2,3-diphenylbenzoquinoxaline (2,3DPQ) has been synthesized and its inhibiting action on the corrosion
Received 28 July 2009 of mild steel in 0.5 M H2SO4 has been assessed by weight loss method at 30 °C. The results of the inves-
Accepted 5 September 2009 tigation show that this compound has excellent inhibiting properties for steel corrosion in sulphuric acid.
Available online 14 September 2009
Inhibition efficiency increases with increase in the concentration of the inhibitor. The adsorption of
2,3DPQ onto the mild steel surface followed the Langmuir adsorption model with the free energy of
Keywords: adsorption DG0ads of 11.4 kJ mol1. Quantum chemical calculations were employed to give further
2,3-Diphenylbenzoquinoxaline
insight into the mechanism of inhibition action of 2,3DPQ.
Corrosion inhibitors
Density functional theory (DFT)
Ó 2009 Elsevier Ltd. All rights reserved.
Adsorption isotherm

1. Introduction
Acid inhibitors are usually used in several processes to control
the corrosion of metals. They find wide applications as components
in cleaning solutions for industrial equipments, and in acidification
of oil wells [1]. Most of the well-known acid inhibitors are organic
compounds containing nitrogen, sulphur and oxygen as well as
aromatic rings in their structure which are the major adsorption
centers [2]. Studies report that the adsorption of organic inhibitors
mainly depends on some physicochemical properties of the mole-
cule, related to its functional groups, to the possible steric effects
and electronic density of donor atoms; adsorption is suppose also
to depend on the possible interaction of p-orbitals of the inhibitor
with d-orbitals of the surface atoms, which induce greater adsorp-
tion of the inhibitor molecules onto the surface of carbon steel,
leading to the formation of a corrosion protecting film [3]. Several
reports have documented the use of many N-heterocyclic com-
pounds, such as benzylaminopurine [4], S-triazole-triazole deriva-
tives, [5], azoles [6], Schiff base [7], pyridine derivatives, [8],
pyrazole derivatives [9], bipyrazole derivatives [10], pyrimidine
derivatives [11], and benzimidazole derivatives [12–14] as effec-
tive corrosion inhibitors for iron/steel in acidic media.
DFT (density functional theory) methods have become very
popular in the last decade due to their accuracy and less time
requirement from the computational point of view [15]. Based on
the well-known Hohenberg–Kohn theorems [16], DFT focuses on
* Corresponding author. Tel.: +234 8067476065.
E-mail address: proffoime@yahoo.com (I.B. Obot).
the electron density, qðrÞ, itself as the carrier of all information
in the molecular (or atomic) ground state. Important molecular
properties of molecules such as EHOMO, ELUMO, dipole moment, Mul-
liken charges, etc., have been correlated with inhibition efficiency
of different inhibitors using DFT [17].
Quinoxaline derivatives are a very important class of nitrogen-
containing compounds and have been widely used in dyes [18],
pharmaceuticals [19], and electrical/photochemical materials
[20]. Quinoxaline ring moiety constitutes part of the chemical
structures of various antibiotics such as Echinomycin, Levomycin
and Actinoleucin [21,22]. Perusal of several literature reveal that
there is no information regarding the use of quinoxaline derivative
(2,3-diphenylbenzoquinixaline) as corrosion inhibitor. This paper
focuses on the inhibition efficiency of 2,3-diphenylbenzoquinixa-
line, which is a derivative of quinoxaline as steel corrosion inhibi-
tor in sulphuric acid. The investigation is performed using
gravimetric measurement as well as quantum chemical calcula-
tions in order to explain the mechanism of the inhibitory action.
2. Experimental
2.1. Materials preparation
The sheet of mild steel used has the same composition as that
earlier reported [3]. The mild steel sheet was mechanically press-
cut into coupons of dimension 5  4  0.07 cm. These coupons
were used as supplied without further polishing. However, surface
treatment of the coupons involved degreasing in absolute in abso-
lute ethanol and drying in acetone. The treated coupons were then

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.09.013
 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 282–285 283

stored in a moisture-free desiccator before their use in corrosion
studies.
The inhibitor 2,3-diphenylbenzoquinixaline (Fig. 1) was pre-
pared according to Brown [23]. Benzil (0.105 g, 0.5 mmol), 2,3-dia-
minonaphthalene (0.078 g, 0.5 mmol), each dissolved in (10 ml) of
twice distilled ethanol were mixed and refluxed for 35 min, then
poured into a beaker of water to precipitate. The precipitate was
filtered and washed with ethanol. It was then recrystallized twice
from absolute ethanol and dried over P2O5 under vacuo. Inhibitor
concentrations of 2  106 to 10  106 M were prepared in
0.5 M H2SO4 solution at 30 °C.
performed in triplicate to guarantee the reliability of the results
and the mean value of the weight loss is reported. The reproduc-
ibility of the experiment was higher than 95%. Weight loss allowed
calculation of the mean corrosion rate in mg cm2 h1.
2.3. 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
exchange terms associated with the gradient corrected correlation

2.2. Weight loss determination a 100

Gravimetric experiments were carried out as earlier reported 95

[1,2]. The maximum duration of tests was 24 h at 30 °C in non-
de-aerated solutions. At the end of the tests, the coupons were im-
90

E(%)
mersed in 20% NaOH solution containing 200 g/l of zinc dust,
scrubbed with bristle brush under running water in order to re-
move the corrosion product, dried and re-weighed. The tests were 85

80

75
2 4 6 8 10
N -6
C(M) x 10

b 100

95
N
90

85
E (%)

80
Fig. 1. Chemical structure of 2,3-diphenylbenzoquinixaline.
75

70
Table 1 65
Corrosion parameters for mild steel in 0.5 M H2SO4 in the absence and presence of
different concentrations of 2,3-diphenylbenzoquinoxaline at 30 °C. 60
2 1 4 8 12 16 20 24
System/concentration Corrosion rate (mg cm h ) IE (%)
t (h)
Blank 89.4 ± 2.8 –
2  106 M 16.1 ± 0.3 81.99
Fig. 3. Variation of inhibition efficiency against (a) concentration and (b) immer-
4  106 M 9.8 ± 0.2 89.04
sion time for 2,3DPQ at 30 °C.
6  106 M 9.6 ± 0.5 89.28
8  106 M 7.4 ± 0.7 91.78
10  106 M 0.9 ± 0.9 98.99
12

3.5 10
Blank 2 x 10 ^-6

3 4 x 10 ^-6 6 x 10 ^-6
8
Weight loss (g/cm 2)

8 x 10 ^-6 10 x 10 ^-6
C/ θ (M) x 10-6

2.5
6
2

1.5 4

1
2
0.5

0 0
4 8 12 16 20 24 2 4 6 8 10
-6
Immersion time (h) C(M) x 10

Fig. 2. Weight loss-time curves for mild steel corrosion without and with varying Fig. 4. Langmuir adsorption plot for mild steel in 0.5 M H2SO4 containing different
concentrations of 2,3DPQ at 30 °C. concentrations of 2,3DPQ.
284 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 282–285

functional of Lee, Yang, and Parr (LYP) [24], has been recognized 3. Results and discussion
especially for systems containing transition metal atoms [25]. It
has much less convergence problems than those commonly found The corrosion of mild steel in 0.5 M H2SO4 solution containing
for pure DFT methods. Thus, B3LYP was used in this work to carry various concentrations of inhibitor was studied by weight loss
out quantum calculations. Then, full geometry optimization of the measurements.
inhibitor was carried out at the B3LYP/6-31G(d) level using the The corrosion rate of mild steel was determined using the
Spartan’06 V112 program package. relation

Fig. 5. (a) Optimized molecular structure of 2,3-diphenylbenzoquinoxaline (ball and stick models) (b) the highest occupied molecular orbital (HOMO) density of 2,3-
diphenylbenzoquinoxaline and (c) Mulliken population analysis of 2,3-diphenylbenzoquinoxaline.
 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 282–285
Dm
W¼
St
where Dm is the mass loss, S the area and t is the immersion period.
The percentage inhibition efficiency (E(%)) was calculated using
the relationship
 
W corr  W corrðinhÞ
Eð%Þ ¼  100
W corr
where W corr and W corrðinhÞ are the corrosion rates of mild steel in the
absence and presence of 2,3DPQ, respectively. Table 1 gives the val-
ues of the corrosion parameters for mild steel in 0.5 M H2SO4 in the
absence and presence of different concentrations of 2,3-diph-
enylbenzoquinoxaline at 30 °C after 4 h of immersion. Fig. 2 shows
the weight loss-time curves for mild steel corrosion without and
with varying concentrations of 2,3DPQ at 30 °C. Inspection of the
figure shows that the weight loss of mild steel varies linearly with
time and was reduced in the presence of the inhibitor compared
to the free acid solution. This attest to the fact that 2,3DPQ actually
inhibited the corrosion of mild steel in 0.5 M H2SO4.
Fig. 3(a) shows the plot of inhibition efficiency against the dif-
ferent concentrations of 2,3DPQ. The results showed that inhibi-
tion efficiency increased as the concentration of inhibitor rose
from 2  106 to 10  106 M. Further increases of inhibitor con-
centration provide a lower degree of protection. The concentration
of 10  106 M was found to be the optimum concentration for the
inhibitor. Fig. 3(b) shows the variation of inhibition efficiency as a
function of immersion time. It is evident from the figure that inhi-
bition efficiency decreases with the increase in the immersion time
from 4 to 24 h indicating the instability of inhibitor film on the me-
tal surface up to 24 h. Similar reports have been documented [26].
Basic information on the interaction between the inhibitors and
the steel surface is provided by the adsorption isotherm. The de-
gree of surface coverage, h, at different inhibitor concentrations
in 0.5 M H2SO4 was evaluated from weight loss measurements
(h = IE(%)/100) at 30 °C. The plot of C/h against inhibitor concentra-
tion C displayed a straight line for tested inhibitor (Fig. 4). The lin-
ear plot with high correlation coefficient (0.994) clearly revealed
that the surface adsorption process of 2,3DPQ on the mild steel sur-
face obeys the Langmuir isotherm. Likewise, it suggests that an
adsorption process occurs [3], which can be expressed as follows
[16]:
C 1
¼ þC
h K ads
where K ads is the equilibrium constant of the adsorption process.
Free energy of adsorption (DGads ) can be calculated by Eq. (4). The
numeral of 55.5 is the molar concentration of water in the solution:
! [15]
1 DG0ads
K ads ¼ exp
55:5 RT
The value of DG0ads for adsorption of 2,3DPQ was found to be
11.4 kJ mol1. The negative value of DG0ads suggests that 2,3DPQ is
spontaneously adsorbed on the mild steel surface. Literature survey
reveals that the values of DG0ads around 20 kJ mol1 or lower are
consistent with the electrostatic interaction between the charged
molecules and the charged metal (physical adsorption) [27].
The adsorption of an inhibitor on the metal surface can occur on
the basis of donor–acceptor interactions between the p-electrons
of the heterocyclic compound and the vacant d-orbitals of the me-
tal surface atoms [3], so the energies of the frontier orbitals should
be considered. Energy of LUMO depicts the ability of the molecule
to receive charge when attacked by electron pair donors, even as
285
the energy of HOMO to donate the charge when attached by elec-
ð1Þ
tron seeking reagents. As the energy gap between the frontier orbi-
tals get smaller, the interactions between the reacting species get
stronger [28]. The highest occupied molecular orbital density is
plotted as given in Fig. 5. HOMO location in the 2,3DPQ molecule
is mostly distributed in the vicinity of the nitrogen atoms and
the aromatic rings of the benzoquinoxaline moiety. This indicates
ð2Þ
the reactive sites of the interaction between 2,3DPQ and the mild
steel surface.
The further provide evidence that the nitrogen atoms in 2,3DPQ
were the main center of adsorption with the steel surface, Mulliken
population analysis was carried out (Fig. 5). It is clear from the fig-
ure that the nitrogen atoms of 2,3DPQ have considerable excess of
negative charge than other atoms. Thus, the adsorption of 2,3DPQ
as neutral molecules on the metal surface can occur directly
involving the displacement of water molecules from the metal sur-
face and sharing of electrons between the nitrogen atoms and the
metal surface. It should be noted that 2,3DPQ adsorb mainly
through electrostatic interactions between the positively charged
nitrogen atom (since acidic solution can protonate the nitrogen
atoms of 2,3DPQ) and the negatively charged metal surface (phys-
isorption) as evident in the value of DG0ads obtained. Similar obser-
vation has been reported [1].
4. Conclusions
1. The compound namely 2,3DPQ shows good performance as cor-
rosion inhibitor in 0.5 M H2SO4.
2. The 2,3DPQ inhibits the corrosion by getting adsorbed on the
metal surface following Langmuir adsorption isotherm.
3. Quantum chemical calculations show that the adsorption sites
are mainly located around the nitrogen atoms of 2,3DPQ.
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