Corrosion Science 51 (2009) 1868–1875

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

Antifungal drugs as corrosion inhibitors for aluminium in 0.1 M HCl

I.B. Obot a,*, N.O. Obi-Egbedi b, S.A. Umoren a
a
Department of Chemistry, Faculty of Science, University of Uyo, Uyo, 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 inhibitive capabilities of Clotrimazole (CTM) and Fluconazole (FLC), two antifungal drugs, on the elec-
Received 28 February 2009 trochemical corrosion of aluminium in 0.1 M HCl solution has been studied using weight loss measure-
Accepted 15 May 2009 ments at 30 and 50 °C. The results indicate that both compound act as inhibitors in the acidic corrodent.
Available online 21 May 2009
At constant acid concentration, the inhibition efficiency (%I) increased with increase in the concentration
of the inhibitors. Increase in temperature increased the corrosion rate in the absence and presence of the
Keywords: inhibitors but decreased the inhibition efficiency. CTM and FLC adsorbed on the surface of aluminium
Clotrimazole
according to the Langmuir adsorption isotherm model at all the concentrations and temperatures stud-
Fluconazole
A. Aluminium
ied. Phenomenon of physical adsorption is proposed from the activation parameter obtained. Thermody-
Corrosion inhibition namic parameters reveal that the adsorption process is spontaneous. The reactivity of these compounds
Adsorption isotherm was analyzed through theoretical calculations based on AM1 semi-empirical method to explain the dif-
ferent efficiencies of these compounds as corrosion inhibitors. CTM was found to be a better inhibitor
than FLC.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction Compounds with functional groups containing hetero-atoms,

Corrosion of aluminium and mainly its alloys has been a subject
of numerous studies due to their high technological value and wide
range of industrial applications especially in aerospace and house-
hold industries. Aluminium and its alloys, however, are reactive
materials and are prone to corrode. Aluminium relies on the forma-
tion of a compact, adherent passive oxide film for its corrosion
immunity in various environments. This surface film is amphoteric
and dissolves substantially when the metal is exposed to high con-
centrations of acids or bases [1]. In an attempt to mitigate electro-
chemical corrosion of aluminium, the main strategy is to
effectively isolate the metal from corrosion agents. This can be
achieved by the use of corrosion inhibitors. The use of inhibitors
is one of the best known methods of corrosion protection. Organic
compounds used as inhibitors act through a process of surface
adsorption, so the efficiency of an inhibitor depends not only on
the characteristics of the environment in which it acts, the nature
of the metal surface and electrochemical potential at the interface,
but also on the structure of the inhibitor itself, which includes the
number of adsorption active centers in the molecule, their charge
density, the molecular size, the mode of adsorption, the formation
of metallic complexes and the projected area of the inhibitor on the
metal surface [2,3].
* Corresponding author. Address: Department of Chemistry, Faculty of Science,
University of Uyo, P.M.B. 1017, Uyo, Akwa Ibom State, Nigeria. Tel.: +234
8023223256.
E-mail address: proffoime@yahoo.com (I.B. Obot).
which can donate lone pairs of electrons are found to be particu-
larly useful as inhibitors for metal corrosion [4–9]. Also com-
pounds with p-bonds also generally exhibit good inhibitive
properties by providing electrons to interact with the metal surface
[10–15]. Both features obviously can be combined within the same
molecule such as drugs.
For proper selection of inhibitors, chemical and electrochemical
techniques coupled with surface analytical techniques can be used
but a need exists for a systematic approach for characterization of
the interaction between the organic inhibitor molecules and the
metal surfaces in order to search new and efficient corrosion inhib-
itors. Theoretical approaches provide means of analyzing these
interactions and there are many reports related with this area
[16–25]. The molecular structure and the electronic parameters
that can be obtained through theoretical calculations as the
HOMO (higher occupied molecular orbital) energy, the LUMO
(lower unoccupied molecular orbital) energy, the energy of the
gap (DE = ELUMO  EHOMO), are involved in the activity of the
inhibitors.
In recent years, owing to the growing interest and attention of
the world towards environmental problems and towards the pro-
tection of environment and the hazardous effects of the use of
chemicals on ecological balance, the traditional approach on the
choice of corrosion inhibitors has gradually changed [26]. Re-
searches are mainly focusing on non-toxic ‘‘green” corrosion inhib-
itors [27–29]. Clotrimazole (CTM) and Fluconazole (FLC) which is
the object of the present investigation are non-toxic, cheap and
environmental friendly antifungal drugs that are use in the treat-

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.05.017
 I.B. Obot et al. / Corrosion Science 51 (2009) 1868–1875 1869

ment of fungal disease. They contain reactive centers like N atoms 0.07
1 x 10-4
containing lone pairs of electrons and aromatic rings with delocal- 8 x 10-5 (a)
0.06
ize p electron systems which can aid their adsorption onto metal 6 x 10-5
4 x 10-5
surfaces. Furthermore, they have high molecular weights and are 0.05

Weight loss(g)
2 x 10-5
likely to effectively cover more surface area (due to adsorption) Blank
0.04
of the metal thus preventing corrosion from taking place. Thus,
the present study was undertaken to compare the inhibitive abili- 0.03
ties of Clotrimazole and Fluconazole (Fig. 1) on aluminium corro-
0.02
sion in hydrochloric acid solution using weight loss method at 30
and 50 °C. Quantum chemical calculations were further employed 0.01
to explain the different efficiencies of these compounds as corro-
0
sion inhibitors.
1 2 3 4 5 6 7

Time (d ays)

0.07
1 x 10-4 (b)
0.06 8 x 10-5
6 x 10-5
4x 10-5
Cl 0.05 2 x 10-5

Weight loss(g)
Blank

N 0.04

N
0.03

0.02

0.01

0
1 2 3 4 5 6 7

1-[(2-chlorophenyl)-diphenyl-methyl]imidazole Tim e (days)

Clotrimazole (CTM) Fig. 1. Plots of weight loss against time for (a) CTM and (b) FLC at 30 °C.

N N
F N
N ven time and the initial weight of the test coupon determined
N were performed in duplicate to guarantee the reliability of the re-
N
F allowed calculation of the mean corrosion rate in mg cm2 h1.
HO
2-(2,4-difluorophenyl)-1,3-bis(1H-1,2,4-triazol-1-yl)-2-propanol
Fluconazole (FLC)
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 and 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 [30].
All reagents used were BDH analytical grade. They were used as
sourced without further purification. An aqueous solution of 0.1 M
HCl was used as a blank solution. Clotrimazole and Fluconazole,
which were obtained commercially from May and Baker pharma-
ceuticals, were added to the acid in concentrations ranging from
2  105  1  104 M. Experiments were conducted in the test
solutions for 24 h progressively for 168 h (7 days) at 30 and 50 °C
in non-de-aerated solutions. In each experiment, the cleaned alu-
minium coupon was weighed and suspended with the aid of glass
rod and hook in a beaker containing 100 ml acid solution. The cou-
pon was then taken out of the test solution, washed in 70% nitric
acid for 2 min to remove the corrosion products using bristle
brush, rinsed with distilled water, dried and re-weighed. The
weight loss was taken as the difference between the weight at a gi-
using LP 120 digital balance with sensitivity of ±1 mg. The tests
sults and the mean value of the weight loss is reported. Weight loss
Semi-empirical methods serve as efficient computational tools
which can yield fast quantitative estimates for a number of proper-
ties. This may be particularly useful for correlating large sets of
experimental and theoretical data, for establishing trends in clas-
ses of related molecules, and for scanning a computational prob-
lem before proceeding with higher level treatment. AM1 (Austin
model 1) is a semi-empirical method based on the neglect of differ-
ential diatomic overlap integral approximation. Specifically, it is a
generalization of the modified neglect of diatomic differential
overlap approximation. AM1 was developed by Michael Dewar
and co-workers reported in 1985 [31]. AM1 is an attempt to im-
prove the MNDO model (Modified neglect of differential overlap)
by reducing the repulsion of atoms at close separation distances.
The atomic core-atomic core terms in the MNDO equations were
modified through the addition of off-center attractive and repul-
sive Gaussian functions. The complexity of the parameterization
problem increased in AM1 as the number of parameters per atom
increased from seven in MNDO to 13–16 per atom in AM1 [32]. The
quantum chemical calculation was performed using Spartan’06
V112 semi-empirical program. AM1 semi-empirical method was
employed to obtain the optimized geometry. The level of theory
(AM1) used in this work has been reported by us and others and
was shown to give good results [33,34–36].
1870 I.B. Obot et al. / Corrosion Science 51 (2009) 1868–1875

3. Results and discussion
3.1. Corrosion rates and inhibition efficiency
The weight loss method of monitoring corrosion rate is useful
because of its simple application and reliability [33]. Weight loss
of aluminium were determined after 168 h (7 days) of immersion
in 0.1 M HCl in the absence and presence of various concentrations
of Clotrimazole (CTM) and Fluconazole (FLC) at 30 and 50 °C,
respectively.
The corrosion rate (v ) was calculated from the following equa-
tion [37]:
v ¼ ðm1  m2 Þ=St;
where m1 is the mass of the Al coupon before immersion in (mg), m2
the mass of the Al coupon after immersion in (mg), S is the total
area of the Al coupon (cm2), t is the corrosion time in (h) and v is
the corrosion rate in (mg cm2 h1). The calculated corrosion rate
(v) in Eq. (1) is an average corrosion rate as no localized corrosion
takes place.
With the corrosion rate, the percentage inhibition efficiency (%I)
was calculated using the following equation [38]:
%I ¼ ðv 0  v Þ=v 0  100;
where v 0 and v are the corrosion rates of the Al coupon in 0.1 M HCl
in the absence and presence of CTM and FLC, respectively.
Fig. 1 shows a representative plot of weight loss against time
(days) for Al in 0.1 M HCl in the absence and present of different
concentrations of (a) CTM and (b) FLC at 30 °C. Similar plots were
obtained for 50 °C. The figure clearly shows a reduction in weight
loss of the metal coupons in the presence of the two inhibitors
compared to the blank. Moreover a higher reduction in weight loss
was observed for CTM compared to FLC. Table 1 shows the calcu-
lated values of corrosion rates obtained using Eq. (1) as well as
inhibition efficiency values evaluated using the expression given
in Eq. (2). It is clearly seen from the table that corrosion rates were
reduced in the presence of CTM and FLC compared to their absence
for aluminium corrosion in 0.1 M HCl. Also corrosion rates were
observed to increase with increase with the temperature both in
the absence and presence of inhibitors. Corrosion rates values are
also seen to decrease with increase in concentration. This actually
shows that the addition of CTM and FLC, respectively, to the acid
solution retard the corrosion rate of aluminium and that the extent
of retardation is concentration dependent. Similar observations
have been documented [4,33].
The electrochemical theory of corrosion proposed that corro-
sion of metals is largely accomplished by the action of a network
of short-circuited electrolytic cells on the metal surfaces [39]. Alu-
minium ions go into solution at the anodes of these cells in amount
chemically equivalent to the reaction at the cathodes. The anodic
dissolution reaction of aluminium in hydrochloric acid solution is
as follows:
3þ
Al ! Al þ 3e : ð3Þ
On the other hand, the reaction at the cathodes which lead to
hydrogen evolution can be represented as:
Hþ þ e ! Hads ð4Þ
Hads þ Hads ! H2 : ð5Þ
Thus, Eqs. (3)–(5) lead to the corrosion of aluminium in hydro-
chloric acid solution. Considering the inhomogeneous nature of
ð1Þ metallic surfaces resulting from the existence of lattice defects
and dislocations, a corroding metal surface is generally character-
ized by multiple adsorption sites having definite activation ener-
gies and heat of adsorption. Inhibitor molecules may thus, be
adsorbed more readily at the surface active sites having suitable
adsorption enthalpies [40].
Inhibition efficiency as given in Table 1 is found to increase with
increase in concentration but decrease with increase in tempera-
ture for CTM and FLC, respectively. Inhibition efficiency increases
with inhibitor concentration to reach 88.25% for CTM and 82.40%
ð2Þ for FLC at 1  104 M, respectively. Increased inhibition efficiency
with concentration indicates that more CTM and FLC components
are adsorbed on the aluminium surface at higher concentration,
leading to greater surface coverage. Similar observations have been
reported [1,4]. Both CTM and FLC inhibit the corrosion of alumin-
ium in 0.1 M HCl in the range of concentrations studied but CTM
is found to be more effective than FLC at the two temperature
studied.
The higher values of inhibition efficiency observed for CTM over
FLC may be explained by the presence of aromatic rings, and nitro-
gen atoms with lone pair of electrons, and the p-electrons of the
imidazole moiety which serves as adsorption centers for their
interaction with the metal surface. This supersedes the effect of
one Cl atom on the aromatic ring of CTM. On the other hand, the
presence of electron withdrawing groups like F atoms and OH
group (due to mesomeric effect), makes electron density less avail-
able for FLC. Halogens have been known to deactivate benzene
rings [41]. This leads to weak adsorption and by extension inhibi-
tion as less electron density is made available to the aluminium
surface for coordinate bonding since inhibitors are adsorbed on
metal surfaces through donor–acceptor type reaction [42]. Thus,
the better inhibition performance of CTM with comparison to FLC
could be correlated to the presence of increased electron density
at the active centers in the molecule. This assertion is confirmed
with the value of HOMO energy calculated for CTM (Section 3.5).
The observed inhibition efficiencies of CTM and FLC apart from
depending on their molecular structure may also depend on many

Table 1
Corrosion parameters for aluminium in 0.1 M HCl in the absence and presence of different concentrations of Clotrimazole (CTM) and Fluconazole (FLC) at different temperatures.

Inhibitor System/concentration Corrosion rate (mg cm2 h1) (%I)

30 °C 50 °C 30 °C 50 °C
CTM Blank 35.4 372.9 – –
2  105 M 14.6 237.5 58 36
4  105 M 11.3 225.0 68 39
6  105 M 8.4 214.6 76 42
8  105 M 6.2 206.3 82 44
1  104 M 4.2 200.0 88 46
FLC 2  105 M 16.7 300.0 52 19
4  105 M 12.5 295.8 64 21
6  105 M 10.4 289.6 70 22
8  105 M 8.3 279.2 76 25
1  104 M 6.3 270.8 82 27
 I.B. Obot et al. / Corrosion Science 51 (2009) 1868–1875 1871

other factors such as the number of adsorption active centers in the

molecule and their charge densities, molecular size, mode of
adsorption, heat of hydrogenations and formation of metallic com-
plex and the projected area of the inhibitor on the metal surface
[2,3,42]. More so, as far as inhibition process is concern, it is gen-
erally assumed that adsorption of the inhibitor at the metal/solu-
tion interface is the first step in the action mechanism of the
inhibition in the aggressive acid media. The adsorption mechanism
for a given inhibitor depend on such factors as the nature of metal
and corrosive medium, the pH and the concentration of the inhib-
itor as well as the functional groups present in its molecule, since
different groups are adsorbed to different extents [43]. A step to-
wards improving further the inhibition efficiency of CTM and FLC Fig. 2. Langmuir adsorption plot for Clotrimazole at 30 and 50 °C.
through the addition of halide ions is currently being investigated
in our laboratory.
The decrease in inhibition efficiency with increase in tempera-
ture as observed in this study (Table 1) for CTM and FLC, respec-
tively, is suggestive of physisorption mechanism usually
attributed to electrostatic interaction between charged molecules
and the charged metal. This observation has been explain to be
due to reduction in stability of adsorbed film at higher tempera-
tures; as temperature increases, Gibbs free energy and enthalpy
rises to a higher value, so that some of the chemical bonds joining
the molecules onto the metallic surface are impaired and film sta-
bility reduced [44].

3.2. Adsorption consideration

It is a widely held view by many authors that the adsorption of
organic inhibitor molecules is often a displacement reaction
involving the removal of adsorbed water molecules from the metal
surface [1,5,45]:
OrgðsolÞ þ xH2 OðadsÞ ¡ OrgðadsÞ þ xH2 OðsolÞ :
In general, the proceeding of physical adsorption requires the
presence of both electrically charged surface of the metal and
charged species in the bulk of the solution. Chemisorption process
involves charge sharing or charge transfer from the inhibitor mol-
ecules to the metal surface to form a co-ordinate type of a bond.
This is possible in case of a positive as well as a negative charge
of the metal surface [46].
Perusals of literatures show that organic compounds act as an
inhibitor by adsorption on the metal surface. Inhibitor molecules
may adsorb on the aluminium surface in the form of:
(i) Neutral molecule via chemisorption mechanism involving
the sharing of electrons between the heteroatom and
aluminium.
(ii) Adsorption of inhibitor can occur through p-electron inter-
actions between the aromatic ring of the molecule and the
metal surface.
(iii) Cationic form with positively charged part of the molecule is
oriented towards negatively charged aluminium surface
[47]. Adsorption can also occur via electrostatic interaction
between a negatively charged surface, which is provided
with a specifically adsorbed anion on aluminium and posi-
tive charge of the inhibitor.
Fig. 3. Langmuir adsorption plot for Fluconazole at 30 and 50 °C.
The adsorption isotherm experiments were performed to have
more insights into the mechanism of corrosion inhibition, since it
ð6Þ describes the molecular interaction of the inhibitor molecule with
the active sites on the aluminium surface [48]. The degree of sur-
face coverage (h) was evaluated from the weight loss measure-
ments [49]:
%I
h¼ : ð7Þ
100
It is necessary to determine empirically which adsorption iso-
therm fits best to the surface coverage data in order to use the cor-
rosion rate measurements to calculate the thermodynamic
parameters pertaining to inhibitor adsorption. Attempts were
made to fit surface coverage values into different adsorption iso-
therm models. The models considered were [50]:
Temkin isotherm expðf  hÞ ¼ K ads C ð8Þ
Langmuir isotherm h=ð1  hÞ ¼ K ads C ð9Þ
Frumkin isotherm h=ð1  hÞ  expð2f  hÞ ¼ K ads C ð10Þ
and Freundlich isotherm h ¼ K ads C; ð11Þ
where K ads is the equilibrium constant of the adsorption process, C
the inhibitor concentration and f the factor of energetic inhomoge-
neity. By far best results were obtained for Langmuir adsorption iso-
therm. The correlation coefficient (R2) was used to choose the
isotherm that best fit experimental data (Table 2). The linear rela-
tionships of C/h versus C, depicted in Figs. 2 and 3, suggest that

Table 2
Calculated thermodynamic parameters from Langmuir adsorption isotherm.

Inhibitor Temperature (°C) Kads (M1) DGads (kJ mol1) Slope R2

Clotrimazole 30 7.820 15.30 2.04 0.984
50 2.370 13.10 4.81 0.993
Fluconazole 30 5.356 14.34 2.11 0.996
50 2.040 12.70 4.90 0.980
1872 I.B. Obot et al. / Corrosion Science 51 (2009) 1868–1875

the adsorption of CTM and FLC on the aluminium surface obeyed Table 3
the Langmuir adsorption isotherm. This isotherm can be repre- Calculated values of activation energy (Ea) and heat of adsorption (Q ads ) for Al
dissolution in 0.1 M HCl in the absence and presence of CTM and FLC at 30 and 50 °C.
sented as:
System/concentration Ea (kJ mol1) Q ads (kJ mol1)
C 1
¼ þ C: ð12Þ CTM
h K ads
Blank 95.92 –
The strong correlation (R2 P 0.98) of the Langmuir adsorption 2  105 M 113.75 77.59
4  105 M 117.78 78.89
for CTM and FLC was observed. This isotherm postulates that there
6  105 M 126.23 81.77
is no interaction between the adsorbed molecules and the energy 8  105 M 130.83 88.73
of adsorption is independent on the surface coverage (h). Lang- 1  104 M 157.77 117.59
muir’s isotherm assumes that the solid surface contains a fixed FLC
number of adsorption sites and each holds one adsorbed species 2  105 M 117.79 61.30
[50]. The slopes of the straight lines obtained from the plots of 4  105 M 128.96 79.10
Langmuir isotherm for CTM and FLC are more than unity. So, it 6  105 M 135.52 87.94
8  105 M 143.15 93.87
could be concluded that each CTM and FLC unit occupies more than 1  104 M 153.63 103.06
one adsorption site on the aluminium surface. A modified Lang-
muir adsorption isotherm [51], could be applied to this phenome-
non, which is given by the corrected equation:
 
C n q2 Ea 1 1
¼ þ nC: ð13Þ log ¼  ; ð15Þ
h K ads q1 2:303R T 1 T 2
This is indicative from some divergence from pure monolayer where q2 and q1 are the corrosion rates at temperature T1 and T2,
adsorption and can be attributed to interactions between adsor- respectively, and R the molar gas constant. An estimate of heat of
bate species on the metal surface as well as changes in the adsorp- adsorption was obtained from the trend of surface coverage with
tion heat with increasing surface coverage [52], factors which were temperature as follows [58]:
not taken into consideration in derivation of the isotherm.
     
h2 h1 T1T 2
The free energy of adsorption DGads of the inhibitors on alumin- Q ads ¼ 2:303R log  log ; ð16Þ
1  h2 1  h1 T2  T1
ium surface can be determined using the following equation [53]:
where h1 and h2 are the degrees of surface coverage at temperatures
DGads ¼ RT lnðK ads  55:5Þ; ð14Þ T1 and T2, The calculated values for both parameters are given in Ta-
where DGads is the standard free energy of adsorption , K ads is the ble 3.
equilibrium constant of adsorption and the value of 55.5 is the con- The relationship between the temperature dependence of per-
centration of water in solution expressed in mol l1. The calculated cent inhibition efficiency (%I) of an inhibitor and the activation en-
DGads and K ads results are also listed in Table 2. The negative values ergy found in its presence was given as follows [59]:
of the DGads indicate the spontaneous adsorption of these molecules
from HCl solution to the metal surface. Values of DGads around (i) Inhibitors whose (%I) decreases with temperature increase.
20 kJ mol1 or lower are consistent with the electrostatic interac- The value of activation energy (Ea) found is greater than that
tion between charged organic molecules and the charged metal sur- in the uninhibited solution.
face (physisorption); those around 40 kJ mol1 or higher involve (ii) Inhibitors whose (%I) does not change with temperature var-
charge sharing or transfer from the organic molecules to the metal iation. The activation energy (Ea) does not change with the
surface to form a co-ordinate type of bond (chemisorptions) [54]. presence or absence of inhibitors.
The values of DGads for both compounds being less than (iii) Inhibitors whose (%I) increases with temperature increase.
40 kJ mol1 indicate physical adsorption. In addition to electro- The value of activation energy (Ea) found is less than that
static interaction, there may be molecular interaction. Also from Ta- in the uninhibited solution.
ble 2, it could be found that the equilibrium constant of the
adsorption process (K ads ) decreased with increasing temperature. While the higher value of the activation energy (Ea) of the pro-
It is well known that K ads designates the adsorption power of inhib- cess in an inhibitor’s presence when compared to that in its ab-
itor onto the aluminium surface. Clearly, CTM and FLC gave high sence according to Umoren [60] is attributed to its physical
values of K ads at lower temperatures, indicating strong adsorption adsorption, its chemisorptions is pronounced in the opposite case.
of CTM and FLC onto the aluminium surface at lower temperatures. The higher value of Ea in the presence of CTM and FLC compared
Thus, the inhibition efficiency decreased with the increase in tem- to that in their absence and the decrease of their %I with tempera-
perature as a result of the desorption of CTM and FLC from the alu- ture increase can be interpreted as an indication of physical
minium surface. Similar observations have been documented adsorption.
[55,56]. The negative Qads values obtained for CTM and FLC indicate that
the degree of surface coverage decreased with rise in temperature,
3.3. Effect of temperature on the inhibition characteristics of CTM and supporting the earlier proposed physisorption mechanism [61].
FLC
3.4. Mechanism of corrosion inhibition with CTM and FLC
To elucidate the mechanism of inhibition and to determine the
activation energies of the corrosion process, weight loss measure- From all indications, the adsorption of CTM and FLC onto the
ments were performed at 30 and 50 °C in the absence and in the aluminium surface is found to be majorly physical in nature. Phys-
presence of the compounds used. The variation of inhibition effi- ical adsorption is as a result of electrostatic attraction between
ciency with temperature is given in Table 1. The apparent activa- charged species in the bulk of the solution. Adsorption of nega-
tion energies (Ea) for the corrosion process in the absence and tively charged species is facilitated if the metal surface is positively
presence of the inhibitors were evaluated from a modified form charged. Positively charged species can also protect the positively
of the Arrhenius equation [57]: charged metal surface acting with a negatively charged intermedi-
 I.B. Obot et al. / Corrosion Science 51 (2009) 1868–1875 1873

ate, such as acid anions adsorbed on the metal surface. Thus in
addition to molecular form, CTM and FLC can also be present as
protonated species in an acid solution. The value of pHzch, which
is defined as the pH at a point of zero charge, is equal to 9.1 for alu-
minium [62]. So aluminium surface is positively charged at pH 1,
which is the pH value of 0.1 M HCl solutions that were used in this
investigation. Thus it can be concluded that CTM and FLC can be
adsorbed onto aluminium surface in two different ways:
(i) The protonated inhibitors electrostatically adsorb onto the
anion covered aluminium surface, through their protonated
form.
(ii) The inhibitors compete with acid anions for sites at the
water covered surface and adsorbed by donating electrons
to the aluminium. Similar observations have been docu-
mented [59,63].
3.5. Quantum chemical studies
energy to remove an electron from the last occupied orbital will
be low [72]. It has also been reported that increasing values of l
may facilitate adsorption (and therefore inhibition) by influencing
the transport process through the adsorbed layer [71].
Table 4 shows that CTM has the highest EHOMO values as com-
pared to FLC. This leads to increase in its adsorption on the alumin-
ium surface and accordingly increases its inhibition efficiency. The
quantum chemical calculations also confirms the lowest values of
ELUMO and DE = ELUMO  EHOMO for CTM when compared to FLC.
This is in a good agreement with the experimental observations
suggesting that CTM has the highest inhibition efficiency when
compared to FLC. The values of dipole moment, molecular area
and molecular mass are highest for CTM than for FLC. This highest
value for the dipole moment of CTM increases its polarizability
[73] whereas the highest values of the molecular area and the
molecular mass enhance effective coverage of CTM molecules onto
the aluminium surface leading to the increase in inhibition
efficiency.

Quantum chemical methods have already proven to be very

useful in determining the molecular structure as well as elucidat- 89

Corrosion inhibition efficiency (%I)

ing the electronic structure and reactivity [64]. Thus, it has become 88
a common practice to carry out quantum chemical calculations in 87
CTM
corrosion inhibition studies. The concept of assessing the efficiency
86
of a corrosion inhibitor with the help of computational chemistry is
85
to search for compounds with desired properties using chemical
intuition and experience into a mathematically quantified and 84
computerized form. Once a correlation between the structure 83
and activity or property is found, any number of compounds 82
including those not yet synthesized, can be readily screened FLC
81
employing computational methodology [65] and a set of mathe-
80
matical equations which are capable of representing accurately
79
the chemical phenomenon under study [66,67].
-9.95 -8.97
The computation of some of the quantum chemical parameters
HOMO Energy (eV)
such as the energies of the molecular orbitals, EHOMO (highest occu-
pied molecular energy) and ELUMO (lowest unoccupied molecular Fig. 4. Correlation of HOMO energy with percent inhibition efficiency of CTM and
orbital energy), DE = ELUMO  EHOMO (energy of the gap), l (dipole FLC.
moment) as well as some other structural parameters have been
determined for possible relations with the inhibitor efficiency of
CTM and FLC and listed in Table 4. 89
EHOMO is often associated with the electron-donating ability of
Corrosion inhibition efficiency (%I)

88
the molecule. Several researches have shown that the adsorption CTM
87
of an inhibitor on the metal surface can occur on the basis of do-
nor–acceptor interactions between the p-electrons of the hetero- 86
cyclic compound and the vacant d-orbital of the metal surface 85
atoms [68–70]. High values of EHOMO show a tendency of the mol- 84
ecule to donate electrons to appropriate acceptor molecules with
83
low energy, empty molecular orbitals. Increasing values of EHOMO
82
facilitate adsorption and therefore enhance the inhibition effi- FLC
ciency, by influencing the transport process through the adsorbed 81
layer [71]. The energy of the lowest unoccupied molecular orbital 80
indicates the ability of the molecule to accept electrons. The lower 79
the value of ELUMO, the more probable it is that the molecule would
-0.69 -0.14
accept electrons. Concerning the value of the energy of the gap
LUMO Energy (eV)
DE = ELUMO  EHOMO, larger values of the energy difference will pro-
vide low reactivity to a chemical species. Lower values of the en- Fig. 5. Correlation of LUMO energy with percent inhibition efficiency of CTM and
ergy difference will render good inhibition efficiency, because the FLC.

Table 4
Quantum chemical indices of CTM and FLC.
0
Inhibitor EHOMO (eV) ELUMO (eV) DE (eV) l (Debye) Area (Å
A) Mol. Wt. (amu)
CTM 8.97 0.69 8.28 3.68 342.9 344.8
FLC 9.95 0.14 9.81 2.46 300.0 306.27
1874 I.B. Obot et al. / Corrosion Science 51 (2009) 1868–1875

89 1. CTM and FLC inhibit the corrosion of aluminium in 0.1 M HCl.

Corrosion inhibition efficiency (%I)

88 CTM is found to be more effective.

CTM 2. The inhibition efficiency increases with increase in inhibitors
87
concentration to attain a maximum value of 88% for CTM at
86
1  104 M. However, inhibition efficiency was found to
85
decrease with increase in temperature for CTM and FLC,
84 respectively.
83 3. The adsorption of both inhibitors CTM and FLC on the alumin-
82 ium surface obeyed the Langmuir adsorption isotherm model.
FLC
81 4. Phenomenon of physical adsorption is proposed from the acti-
80
vation and thermodynamic parameters obtained for both
inhibitors.
79
5. Quantum chemical calculation was used to probe the relation-
8.28 9.81
ship between inhibition efficiency of aluminium in 0.1 M HCl
LUMO Energy - HOMO Energy (eV)
and the EHOMO, ELUMO, ELUMO  EHOMO and the dipole moment.
Fig. 6. Correlation of HOMO–LUMO energy gaps with percent inhibition efficiency The inhibition efficiency increased with increase in EHOMO and
of CTM and FLC. decrease in ELUMO  EHOMO. CTM had the highest inhibition effi-
ciency because it had the highest HOMO energy and lowest
value of ELUMO  EHOMO.

89
Corrosion inhibition efficiency (%I)

88
87
86
85
84
83
82
FLC
81
80
79
2.46
Dipole moment (D)
Fig. 7. Correlation of dipole moment with percent inhibition efficiency of CTM and
FLC.
The relationship between corrosion inhibition efficiency and
HOMO energy levels for CTM and FLC is plotted in Fig. 4. As clearly
seen in the figure, the inhibition efficiency increased with the EHO-
MO level rising. The same trend is observed for inhibition efficiency
with dipole moment (Fig. 7). In Fig. 5, inhibition efficiency is plot-
ted against the LUMO energy, showing that inhibition efficiency is
reduced with the ELUMO level increase. The relationship between
the inhibition efficiency and the energy gap (DE = ELUMO  EHOMO)
is negative (Fig. 6). The strong linear correlation (R2 = 1 in all cases)
between the molecular orbital energy level (MO) and the corrosion
inhibition efficiency of CTM and FLC (Figs. 4 and 5) proved that the
higher the HOMO energy of the inhibitor, the greater the trend of
offering electrons to unoccupied low lying orbital of the aluminium
metal, and the higher the corrosion inhibition efficiency for alu-
minium in HCl acid solution. In addition, the lower the LUMO en-
ergy, the easier the acceptance of electrons from the aluminium
surface, as the HOMO–LUMO energy gap decreased and the effi-
ciency of the inhibitor improved. Similar reports have been docu-
mented [74].
4. Conclusions
From the overall experimental results and discussion the fol-
lowing conclusions can be deduced:
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