Corrosion Science 51 (2009) 276–282

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

The synergistic inhibitive effect and some quantum chemical parameters

of 2,3-diaminonaphthalene and iodide ions on the hydrochloric acid corrosion
of aluminium
I.B. Obot a,*, N.O. Obi-Egbedi b, S.A. Umoren a
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: The effect of iodide ions on the inhibitive performance of 2,3-diaminonaphthalene (2,3-DAN) in 1 M HCl
Received 12 June 2008 for aluminium corrosion has been studied using hydrogen evolution (gasometry) measurements at 30
Accepted 11 November 2008 and 40 °C. Results obtained showed that the presence of 2,3-DAN molecules in the corrosive medium
Available online 21 November 2008
(1 M HCl solution) inhibits the corrosion process of aluminium and as the concentration of 2,3-DAN
increases the inhibition efficiency also increased at the studied temperatures. A synergistic effect was
Keywords: observed between KI and 2,3-DAN. The experimental results suggest that the presence of iodide ions
2,3-Diaminonaphthalene
in the solutions stabilized the adsorption of 2,3-DAN molecules on the metal surfaces and, therefore
Aluminium
Corrosion inhibition
improve the inhibition efficiency of 2,3-DAN. Phenomenon of physical adsorption is proposed for the
Synergism inhibition and the process followed the Freundlich adsorption isotherm. The activation energy (Ea), heat
Adsorption isotherm of adsorption (Qads) and free energy of adsorption for the corrosion process (DGads) have been evaluated
at the different temperatures and the values support the results obtained. Some quantum chemical
parameters and the Mulliken charge densities for 2,3-diaminonaphthalene were calculated by the AM1
Semi-empirical method to provide further insight into the mechanism of inhibition of the corrosion
process.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Corrosion inhibitors are substances that minimize or prevent
corrosion if they are added at low concentrations in an aggressive
environment. Selection of effective corrosion inhibitors is very
important for an application in which inhibitors are needed regard-
ing what kind of metal or alloy and corrosive environment are
used. Effectiveness of the organic inhibitors depends on their
adsorption rates and covering capabilities on metal surfaces [1].
It has been reported by many authorities that adsorption depends
on the molecular structure, surface charge of a metal and type of
electrolytes [2,3]. Inhibitors are adsorbed by the metal surface im-
mersed in an aqueous phase replacing water molecules adsorbed
by the surface. Electrostatic interaction between an inhibitor mol-
ecules and a metal are prominent during this action of inhibitors.
Electron densities of different functional group or groups, polariz-
ability and electronegativity are main factors in this interaction.
Consequently, a lot of organic compounds with suitable structures
including heteroatoms such as P, S, N or O and/or conjugated dou-
* Corresponding author. Tel.: +234 8023223256.
E-mail address: proffoime@yahoo.com (I.B. Obot).
ble bonds have been reported to inhibit metal corrosion in acidic
media [4–6].
The upgrading of inhibition efficiency of organic compounds in
the presence of some anions, particularly halide ions, have been re-
ported by some authors and was ascribed to a synergistic effect [7–
9]. It is thought that the anions are able to improve adsorption of
the organic cations in solution by forming intermediate bridges be-
tween the metal surface and the positive end of the organic inhib-
itor. Corrosion inhibition synergism thus results from increased
surface coverage arising from ion-pair interactions between the or-
ganic cations and the anions.
Several attempts have been made to predict corrosion inhibi-
tion efficiency with a number of individual parameters obtained
via various quantum chemical calculation methods as a tool for
studying corrosion inhibitors [10–13]. These trials were aimed at
finding possible correlations between corrosion inhibition effi-
ciency and a number of quantum molecular properties such as di-
pole moment (l), highest occupied (EHOMO) and lowest unoccupied
(ELUMO) molecular orbitals and the difference between them
(HOMO–LUMO gap), mulliken charges as well as some structural
parameters.
The present work was designed to study (i) corrosion
inhibition of aluminium in molar hydrochloric acid solutions by

0010-938X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.11.013
 I.B. Obot et al. / Corrosion Science 51 (2009) 276–282
2,3-diaminonaphthalene (2,3-DAN) using hydrogen evolution (gas-
ometric) method; (ii) the effect of iodide ions on the inhibition effi-
ciency of 2,3-diaminonaphthalene; (iii) to evaluate the activation
energy, heat of adsorption,the free energy of the adsorption pro-
cess as well as determining the best adsorption isotherm for the
adsorption of 2,3-DAN onto the aluminium surface and; (iv) using
quantum chemical calculations to know the possible active cen-
tre(s) responsible for the adsorption of 2,3-DAN onto aluminium
surface which will give further insight into the adsorption mecha-
nism of the corrosion process.
2. Experimental details
Aluminium sheets of the type AA 1060 and purity 98.8% were
used in this study. Each sheet was 0.14 cm in thickness was
mechanically press-cut into coupons of dimension 5 cm  4 cm.
These coupons were used as cut without further polishing. They
were however degreased in absolute ethanol, dried in acetone,
and stored in moisture-free desiccators prior to use [14].
All reagents used were BDH analytical grade. They were used as
sourced without further purification. An aqueous solution of 1 M
HCl was used as a blank solution. 2,3-diaminonaphthalene was
added to the acid in concentrations ranging from 1  104 to
6  105 M. The halide salt, potassium iodide (KI, BDH) used was
in the concentration range of 3  103–5  103 M. However,
5  103 M KI was used for the synergistic studies.
The apparatus and procedure for gasometric determination of
corrosion rates have earlier been reported in our previous publica-
tion [15] and described elsewhere [16]. The progress of the corro-
sion reaction was monitored by careful volumetric measurement
of the evolved hydrogen gas at fixed time intervals. Experiments
were conducted at 30 and 40 °C.
All the quantum chemical calculations were performed with
SPARTAN’06 V112 semi-empirical program using AM1 method
[17]. The following quantum chemical indices were considered:
the energy of the highest occupied molecular orbital (EHOMO), the
energy of the lowest unoccupied molecular orbital (ELUMO), DE = E-
LUMO  EHOMO, dipole moment (l), and Mulliken charges of 2,3-
diaminonaphthalene.
It is obvious that one 2,3-DAN molecule contains two nitrogen
molecules with lone pairs of electrons that can serve as adsorption
centres, and a lot of p electrons exist in this molecule making it
suitable for this study (Fig. 1).
3. Results and discussion
3.1. Hydrogen evolution and corrosion rates
The relative rapidity and effectiveness of hydrogen evolution
(gasometric) technique, as well as its suitability for monitoring
in situ, any perturbation by an inhibitor with respect to gas evolu-
tion in metal/corrodent systems have been established by earlier
reports [18,19]. Several authors have reported on comparable
agreement between gasometric technique and other techniques
NH2
NH2
2,3-diaminonaphthalene
Fig. 1. The structure of the inhibitor used in this study.
277
of corrosion monitoring. These include polarization measurement
[16], weight loss [20], and thermometric technique [21].
Corrosion of Al in aqueous solution has been reported [22] to
depend on the concentration of anions in solution. A general mech-
anism for the dissolution of Al metal would be similar to that re-
ported by Oguzie et al. [23]
AlðsÞ þ H2 O $ AlOHads þ Hþ þ e ð1Þ
þ 3þ
AlOHads þ 5H2 O þ H $ Al  6H2 O þ 2e ð2Þ
Al
3þ
þ H2 O $ ½AlOH2þ þ Hþ ð3Þ
½AlOH2þ þ X $ ½AlOHXþ ð4Þ
The controlling step in the metal dissolution is the complexation
reaction between the hydrated cation and the anion present Eq.
(3). In the presence of chloride ions the reaction will correspond to

½AlOH2þ þ Cl ! ½AlOHClþ ð5Þ
The soluble complex ion formed increases the metal dissolution
rate which depends on the chloride concentration.
The free corrosion of aluminium in 1 M HCl was characterized by
rapid effervescence resulting from hydrogen gas evolution and cor-
rosion rates in the absence and presence of 2,3-DAN was studied
using hydrogen evolution measurements. Fig. 2 shows the variation
of volume of hydrogen evolved with time for aluminium in different
concentrations of HCl without 2,3-DAN at 30 °C. Inspection of Fig. 2
shows that the hydrogen evolution starts after a certain time from
the immersion of the aluminium coupon in the test solution. It
may be expected that this time corresponded to the period needed
by the acid to destroy the pre-immersion oxide film and is known
as incubation period. From Fig. 2, it could further be seen that the
volume of hydrogen evolved increased with increase in the concen-
tration of the corrodent (HCl) at 30 °C. Similar trend was observed at
40 °C but with rather higher values. This could be attributed to the
fact that an increase in concentration increased the rate of chemical
reaction. Fig. 3 shows the volume of hydrogen evolved during the
corrosion reaction of aluminium in 1 M HCl containing different
concentrations of 2,3-DAN measured as a function of reaction time
at 30 °C. The plots in Fig. 3 illustrate the decreased deflection of
hydrogen gas evolution rate on introduction of 2,3-DAN into the cor-
rodent, indicating that 2,3-DAN actually affords corrosion inhibition
of aluminium in the acidic environments when compared to the
blank. Similar trend was observed at 40 °C. Further reduction in
the volume of H2 was also observed on the addition of the iodide ions
at 30 °C (Fig. 4). Similar trend was observed at 40 °C, but with higher
values. The rates of H2 gas evolution were observed to decrease with
increasing 2,3-DAN concentration, suggesting that the inhibiting
Fig. 2. Plot of hydrogen evolution against time during aluminium corrosion for
different concentrations of blank at 30 °C.
278 I.B. Obot et al. / Corrosion Science 51 (2009) 276–282

the corrosion rate of Al in HCl decreased with addition of 2,3-

DAN compared to the blank. Further reduction of corrosion rate
was observed with 2,3-DAN in combination with iodide ions. Also,
the corrosion rate decreased with increase in the concentration of
the inhibitor. This is an indication that 2,3-DAN showed a signifi-
cant inhibitive effect on Al corrosion in the acidic environment.

3.2. Inhibition efficiency and adsorption considerations

It is generally accepted that the property of inhibition of the

corrosion of an organic compound is attributed to the molecular
structure. The planarity (p) and the lone electron pairs in the het-
eroatoms are important features that determine the adsorption of
these molecules on the metallic surface. Consequently, in inhibited
solutions, the corrosion rate is indicative of the number of free cor-
rosion sites remaining after some sites have been effectively
blocked by inhibitor adsorption. If it is assumed that corrosion oc-
curs only at the free sites such that the covered sites have negligi-
ble corrosion rates, the degree of surface coverage (h) and hence
Fig. 3. Plot of hydrogen evolution against time during aluminium corrosion in 1 M the inhibition efficiency (%I) can be calculated as follows [18]:
HCl in the absence and presence of different concentrations of 2,3-diaminonaph-
thalene at 30 °C. V 1Ht
h¼1 ð6Þ
V oHt
!
V 1Ht
%I ¼ 1  100 ð7Þ
V oHt

where V 1H is the volume of hydrogen evolved at time ‘‘t” for inhib-

Fig. 4. Plot of hydrogen evolution against time during aluminium corrosion in 1 M
HCl in the presence of 10  105 M 2,3-DAN and various concentrations of 2,3-
DAN + KI at 30 °C.
action was concentration dependent. The volume of H2 evolved at
40 °C was higher than at 30 °C.
Table 1 shows the calculated values of the corrosion rates in the
absence and presence of different concentrations of 2,3-DAN, KI
and 2,3-DAN + KI mixtures. From Table 1, it is clearly seen that
ited solution and V oH that for unhibited solution.
The calculated values of inhibition efficiency (%I), and the de-
gree of surface coverage obtained from hydrogen evolution mea-
surements for Al in 1 M HCl in the absence and presence of
different concentrations of 2,3-DAN, KI, and 2,3-DAN + KI mixtures
are presented in Table 2. Table 2 reveals that inhibition efficiency
increases with increase in inhibitor concentration and decreases
with increase in temperature. This is attributed to the decrease
in the protective nature of the inhibitive film formed on the metal
surface (or desorption of the inhibitor molecules from the metal
surface) at higher temperatures [20]. This suggests physical
adsorption mechanism. Physical (electrostatic) adsorption takes
place when inhibition efficiency decreases with increase in tem-
perature (whereas chemical adsorption takes place when inhibi-
tion efficiency increases with increase in temperature [24].
The observed changes in h are shown in Fig. 5 as a function of
concentration of 2,3-DAN and 2,3-DAN + KI in 1 M HCl at 30 and
40 °C respectively. The linear plots obtained (R2 > 0.9) suggest that
the experimental data fit the Freundlich adsorption isotherm
which is given by [25]:
h ¼ KC n ð8Þ

Table 2
Table 1 Inhibition efficiency (%I) and the degree of surface coverage (h) of aluminium in 1 M
Corrosion rates of aluminium in 1 M HCl in the absence and presence of different HCl in the absence and presence of different concentrations of 2,3-DAN, KI and 2,3-
concentrations of 2,3-DAN, KI and 2,3-DAN + 0.005 M KI at 30 and 40 °C. DAN + 0.005 M KI at 30 and 40 °C.

System Corrosion rate (H2 gas vol ml s1)  103 System Inhibition efficiency (degree of surface coverage)
30 °C 40 °C 30 °C 40 °C
Blank 0.38 0.58 Blank – –
5  103 M KI 0.20 0.40 5  103 M KI 47.6 (0.48) 31.98 (0.32)
4  103 M KI 0.23 0.44 4  103 M KI 38.1 (0.38) 23.60 (0.24)
3  103 M KI 0.25 0.46 3  103 M KI 33.7 (0.34) 16.90 (0.17)
1  104 M 2,3-DAN 0.17 0.35 1  104 M 2,3-DAN 54.9 (0.55) 39.10 (0.39)
8  105 M 2,3-DAN 0.19 0.39 8  105 M 2,3-DAN 48.7 (0.49) 32.70 (0.33)
6  105 M 2,3-DAN 0.21 0.42 6  105 M 2,3-DAN 44.3 (0.44) 27.90 (0.28)
1  104 M 2,3-DAN + KI 0.12 0.30 1  104 M 2,3-DAN + KI 67.4 (0.67) 47.97 (0.48)
8  105 M 2,3-DAN + KI 0.14 0.31 8  105 M 2,3-DAN + KI 61.9 (0.62) 43.00 (0.37)
6  105 M 2,3-DAN + KI 0.17 0.32 6  105 M 2,3-DAN + KI 55.4 (0.55) 41.00 (0.41)
 I.B. Obot et al. / Corrosion Science 51 (2009) 276–282 279

Table 3
Calculated parameters from Freundlich adsorption isotherm.

Inhibitor Temperature (°C) Kads DGads (kJ/mol) R2

2,3-DAN 30 0.393 7.768 0.999
40 0.237 6.707 1.000
2,3-DAN + KI 30 0.384 7.705 0.961
40 0.267 7.015 0.997

From Table 2, it is seen that the inhibition efficiency of 2,3-DAN

Fig. 5. Freundlich adsorption Isotherm for (a) 2,3-DAN and (b) 2,3-DAN + KI at 30
and 40 °C.
where h < n < 1, or
ln h ¼ ln K þ n ln C
C is the concentration of 2,3-DAN and K the equilibrium constant for
adsorption which is evaluated from the intercept of the plots and is
related to the standard free energy of adsorption, DGads by
 
1 DGoads
K¼ exp
55:5 RT
The calculated values of K and DGads are given in Table 3. It is clear
from the table that values of K are low indicating weak interaction
between the inhibitor and the aluminium surface, while the values
of DGads are less than 20 kJ/mol which indicates physical adsorp-
tion of 2,3-DAN on the aluminium surface. Generally values of
DGads less than 20 kJ/mol are consistence with electrostatic inter-
action between the charged metal and the inhibitor which indicates
physisorption [15].
3.3. Effect of iodide ion addition
Halides have been reported to inhibit the corrosion of some
metals in strong acids, and this effect depends on the ionic size
and charge, the electrostatic field set up by the negative charge
of the anion on adsorption sites and the nature and concentration
of the halide ion [26]. It has also been reported [27] that the inhib-
itive effect increases in the order Cl < Br < I, which seems to
indicate that the radii of halide ions may have an important role
to play. For example, the iodide ion (radius: 135 pm) is more pre-
disposed to adsorption than is the bromide ion (radius: 114 pm) or
the chloride ion (radius: 90 pm).
attains a maximum value of 54.9% (1  104 M) at 30 °C. The addi-
tion of 0.005 M KI to the 2,3-DAN solution enhances the value of
inhibition efficiency significantly up to 67.4% (1  104) at 30 °C.
This synergistic effect is found to increase with increase in the con-
centration of 2,3-DAN. The synergistic inhibitive effect brought
about by the concentrations of 2,3-DAN and iodide ions on the cor-
rosion of Al in 1 M HCl can be explained as follows. The strong
chemisorptions of iodide ions on the metal surface is responsible
for the synergistic effect of iodide ion, in combination with 2,3-
DAN in their cationic forms [28]. The inhibitors are then adsorbed
by coulombic attraction on the metal surface where iodide ions are
already adsorbed by chemisorptions. Stabilization of adsorbed io-
dide ions with inhibitors in cationic forms lead to greater surface
coverage and thereby greater inhibition [27].
The synergistic parameters were calculated using the relation-
ship initially given by Aramaki and Hackerman and reported else-
where [29]:
1  I1þ2
S1 ¼ ð11Þ
1  I01þ2
where I1+2 = (I1 + I2); I1 = inhibition efficiency of the halides;
I2 = inhibition efficiency of 2,3-DAN; I0 = measured inhibition effi-
ciency for the 2,3-DAN in combination with iodide ions. S1 ap-
proaches 1 when no interaction between the inhibitor compounds
exists, while S1 > 1 points to a synergistic effect. In the case S1 < 1,
the antagonistic interaction prevails, which may be attributed to
competitive adsorption. Values of S1 for different concentrations
ð9Þ of 2,3-DAN in combination with iodide ion are given in Table 4. S1
values given in Table 4 are more than unity, thereby suggesting that
the enhanced inhibition efficiency caused by the addition of iodide
ions to 2,3-DAN is only due to synergistic effect. Thus it can be sug-
gested that iodide ion (I) is initially adsorbed on the metal surface,
2,3-DAN in the form of cation are then adsorbed by the coulombic
ð10Þ
attraction on the metal surface, where the iodide ions are already
chemisorbed and thus suppresses the self-corrosion rate by the sta-
bilization of the adsorbed anion and by the increase in surface cov-
erage. Furthermore, the organic cation itself is weakly adsorbed on
aluminium, since the metal surface is positively charged in HCl
solution. However, adsorption of iodide ion caused a decrease in
the positive charge of Al due to formation of Al-anion surface bond,
which produces a negative pole, facilitating the adsorption of the
organic cation.
3.4. Effect of temperature
The importance of temperature variation in corrosion study
involving the use of inhibitors is to determine the mode of inhibi-
Table 4
Synergistic parameters (S1).
Concentrations of 2,3-DAN S1
1  104 M 1.512
8  105 M 1.662
6  105 M 1.938
280 I.B. Obot et al. / Corrosion Science 51 (2009) 276–282

tor adsorption on the metal surface. Recently, the use of two tem-
peratures to establish the mode of inhibitor adsorption on a metal
surface has been reported and has been found to be adequate
[30,31]. Thus, the influence of temperature on the corrosion behav-
iour of Al in 1 M HCl in the absence and presence of 2,3-DAN of
varying concentrations and 2,3-DAN + KI mixtures were investi-
gated by hydrogen evolution method at 30 and 40 °C. Therefore,
in examining the effect of temperature on the corrosion process,
the apparent activation energies (Ea) were calculated from the
Arrhenius equation [18]:
 
q2 Ea 1 1
log ¼ 
q1 2:303R T 1 T 2
where q2 and q1 are the corrosion rates at temperature T1 and T2
respectively, and R the molar gas constant. An estimate of heat of
adsorption was obtained from the trend of surface coverage with
temperature as follows [27]:
    
h2 h1
Q ads ¼ 2:303R log  log
1  h2 1  h1
 
T1  T2 1
 kJ mol
T2  T1
where h1 and h2 are the degrees of surface coverage at temperatures
T1 and T2, The calculated values for both parameters are given in
Table 5.
Increased activation energy (Ea) in inhibited solutions compared
to the blank suggests that the inhibitor is physically adsorbed on
the corroding metal surface while either unchanged or lower Ea
in the presence of inhibitor suggest chemisorptions [24]. It is seen
from Table 5 that Ea values were higher in the presence of the addi-
tives compared to that in their absence hence leading to reduction
in the corrosion rates. It has been suggested that adsorption of an
organic inhibitor can affect the corrosion rate by either decreasing
the available reaction area (geometric blocking effect) or by mod-
ifying the activation energy of the anodic or cathodic reactions
occurring in the inhibitor-free surface in the course of the inhibited
corrosion process [32]. The Ea values support the earlier proposed
physisorption mechanism. Hence, corrosion inhibition is assumed
to occur primarily through physical adsorption on the aluminium
surface, giving rise to the deactivation of these surfaces to hydro-
gen atom recombination. Similar results have been reported in ear-
lier publications [24,33].
The negative Qads values indicate that the degree of surface cov-
erage decreased with rise in temperature, supporting the earlier
proposed physisorption mechanism [15].
 
Al þ Cl $ AlClads ðaÞ

AlClads
 þ
þ Cl $ AlCl2 þ 3e ðbÞ
The cathodic hydrogen evolution follows the steps:
Hþ þ e ! Hads ðfastÞ ðcÞ
Hþ þ Hads ! H2 ðdÞ
Protonated 2,3-DAN molecules can electrostatically interact with

AlClads species which are formed in step (a). Thus the oxidation
 þ
reaction of AlClads to AlCl2 as shown by step (b) can be prevented.
This phenomenon is attributable to stabilization of adsorbed halides
ð12Þ ions by means of electrostatic interactions with the inhibitor mole-
cules, resulting in greater surface coverage [21] (Fig. 6). The proton-
ated molecules also adsorbed on the cathodic sites of aluminium in
competition with the hydrogen ions (step (d)). In addition, 2,3-DAN
can be adsorbed from its negatively charged centres such as the
nitrogens of the amino groups, and on the p bonds of the aromatic
systems to positively charged aluminium surface. This enhances the
inhibition efficiency considerably. Similar observation has been
documented for Schiff bases containing Br and Cl atom on the ben-
ð13Þ zene ring [34].
3.6. Theoretical study
The effectiveness of an inhibitor can be related to its spatial
molecular structure, as well as with their molecular electronic
structure [35]. Also there are certain quantum chemical parame-
ters that can be related to the interactions metal-inhibitor. Among
these, we can mention the energy of the HOMO, that is often asso-
ciated with the capacity of a molecule to donate electrons. There-
fore, an increase in the values of EHOMO can facilitate the
adsorption and therefore the inhibition efficiency, by indicating
the disposition of the molecule to donate orbital electrons to an

3.5. Mechanism of corrosion inhibition with 2,3-DAN

In order to be able to predict the adsorption mechanism of pro-

tonated 2,3-DAN to positive charged aluminium surface, corrosion
mechanism of aluminium in hydrochloric acid must be known
[34]. According to this mechanism anodic dissolution of Al follows
the steps:

Table 5
Calculated values of activation energy (Ea) and heat of adsorption (Qads) for Al
dissolution in 1 M HCl in the absence and presence of 2,3-DAN and 2,3-DAN + KI at
30–40 °C.

System/concentration Ea (kJ/mol) Qads (kJ/mol)

Blank 33.34 –
1  104 M 56.95 51.12
8  105 M 56.71 52.69
6  105 M 54.66 55.48
1  104 M+0.005 M KI 72.26 62.17
8  105 M+0.005 M KI 75.34 80.57
6  105 M+0.005 M KI 76.64 40.02 Fig. 6. Schematic representation of adsorption behaviour of 2,3-DAN on aluminium
in 1 M HCl.
 I.B. Obot et al. / Corrosion Science 51 (2009) 276–282 281

Fig. 7. Optimized geometry of 2,3-diaminonaphthalene using AM1.

Table 6
Heat of formation group to heat of formation.

Quantum parameter l (D) EHOMO (eV) ELUMO (eV) EHOMO  ELUMO (eV) Heat of formation group (kJ/mol) Point group
Calculated value 2.90 8.16 0.14 8.02 169.50 C1

appropriate acceptor with empty molecular orbitals. In the same
way low values of the energy gap DE = ELUMO  EHOMO will render
good inhibition efficiencies, because the energy needed to remove
an electron from the last occupied orbital will be low [36]. Simi-
larly, low values of the dipole moment l will favour the accumula-
tion of inhibitor molecules on the metallic surface [36].
The optimized geometry of 2,3-DAN is shown in Fig. 7. From
AM1 electronic energy point of view, the Mulliken charge densities
of 2,3-DAN have been calculated together with some physical char-
acters like the EHOMO, ELUMO, DE = ELUMO  EHOMO, dipole moment,
heat of formation and the molecular point group (Table 6). The
Mulliken charge densities have the following values (Table 7 and
Fig. 8). The results seem to indicate that both the value of the
gap energy DE, as well as the value obtained for the dipole moment
l, favour the 2,3-DAN, implying its effectiveness as a corrosion
inhibitor. Similar results was obtained for 4-amino-1,2,3,5-thia-
triazole (4AT) [37].
The use of Mulliken population analyses to probe the adsorp-
tion centres of inhibitors have been widely reported [38–42]. The
Table 7
Mulliken charges for atoms of 2,3-DAN obtained using AM1.
Atom
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
N1
N2
level of theory (AM1) used in this work has been reported by us
and others and was shown to give good results [43,44]. There is
a general consensus by several authors that the more negatively
charged an heteroatom is the more it can be adsorbed on the metal
surface through donor–acceptor type reaction [45–48]. It has also
been reported that electrophiles attack molecules at sites of nega-
tive charge [49], which means that sites of ionic reactivity can be
estimated from the atomic charges in a molecule. Thus, from the
values of Mulliken charge in Table 7 and Fig. 8, it is possible to ob-
serve that all the nitrogen atoms present a considerable excess of
negative charge (0.327954, 0.307245) for N1 and N2 respec-
tively and negative charges around most carbon atoms of the aro-
matic rings. Accordingly, the 2,3-DAN molecule can be adsorbed on
the Al surface using these active centres leading to the corrosion
inhibition action.
4. Conclusions
1. 2,3-Diaminonaphthalene was found to inhibit aluminium cor-
rosion in 1 M HCl.
2. The corrosion process is inhibited by adsorption of 2,3-DAN on
the Al surface following the Freundlich isotherm and inhibition
Mulliken charge efficiency increased with an increased in the concentration of
the inhibitor but decreased with rise in temperature suggesting
0.1282
0.1357 physical adsorption.
0.1141 3. Addition of iodide ions synergistically increased the inhibition
0.0305 efficiency of 2,3-DAN.
0.0176 4. The presence of 2,3-DAN increased the corrosion activation
0.1220
0.1609
energy and the adsorption heats gave negative values.
0.0000 5. The negative values of the free energy of adsorption is an indi-
0.0521 cation that the process was spontaneous.
0.1861 6. Quantum chemical calculation revealed that the adsorption
0.3279
of 2,3-DAN was mainly concentrated around the nitrogen
0.3072
atoms.
282 I.B. Obot et al. / Corrosion Science 51 (2009) 276–282

Fig. 8. Mulliken charges of 2,3-diaminonaphthalene (AM1).

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