Corrosion Science 52 (2010) 198–204

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

Adsorption properties and inhibition of mild steel corrosion in sulphuric acid

solution by ketoconazole: Experimental and theoretical investigation
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: Ketoconazole (KCZ) has been evaluated as a corrosion inhibitor for mild steel in aerated 0.1 M H2SO4 by
Received 15 March 2009 gravimetric method. The effect of KCZ on the corrosion rate was determined at various temperatures and
Accepted 2 September 2009 concentrations. The inhibition efficiency increases with increase in inhibitor concentration but decrease
Available online 11 September 2009
with rise in temperature. Adsorption followed the Langmuir isotherm with negative values of DG0ads , sug-
gesting a stable and a spontaneous inhibition process. Quantum chemical approach was further used to
Keywords: calculate some electronic properties of the molecule in order to ascertain any correlation between the
Ketoconazole
inhibitive effect and molecular structure of ketoconazole.
Mild steel
Corrosion inhibition
Ó 2009 Elsevier Ltd. All rights reserved.
Quantum chemistry
Sulphuric acid

1. Introduction Unfortunately most of the organic inhibitors are toxic, very

Metals and their alloys are exposed to the action of acids in the
industries. Processes in which acid play a very important part are
acid pickling, chemical and electrochemical etching, industrial acid
cleaning, cleaning of oil refinery equipment, oil well acidizing and
acid descaling [1]. Mineral acids are pumped into the well to
counteract formation of plugging by clays and fines or dissolved
carbonates and to remove scale from the bore well and other down-
ward equipments in the acidization operation of oil well from
enhanced oil recovery. The exposure can be most severe but in many
cases, corrosion inhibitors are widely used in industries to prevent or
reduce corrosion rates of metallic materials in these acid media.
Despite continuing advances in the formulation of corrosion resis-
tance materials, the use of chemical inhibitors often remains the
most practical and cost effective means of preventing corrosion.
The use of organic substances to inhibit corrosion of metals in
acidic environments is well established [2–8]. Most of the effective
and efficient organic inhibitors were those compounds that had p
bonds and contained hetero-atoms such as oxygen, nitrogen, sul-
phur, and phosphorus which allowed adsorption on the metal sur-
face [9–12]. The organic inhibitors function through adsorption on
the metal surface blocking the active sites by displacing water mol-
ecules and forming a compact barrier film to decrease the corro-
sion rate.
* Corresponding author. Tel.: +234 8067476065.
E-mail address: proffoime@yahoo.com (I.B. Obot).
expensive and environmentally unfriendly. Due to increasing envi-
ronmental awareness and adverse effect of some chemicals, re-
search activities in recent times are geared towards developing
cheap, non-toxic and environmentally acceptable corrosion inhib-
itors. As an antifungal drug, ketoconazole (KCZ) with a brand name
of Nizoral (Fig 1) was found to be a heterocyclic compound con-
taining N, O, and aromatic rings containing several p bonds which
could possibly serve as active sites for the adsorption process. Fur-
thermore, the molecule is big enough (molecular weight 508.4)
and likely to effectively cover more surface area (due to adsorp-
tion) of the mild steel. Besides, KCZ is very cheap and easily avail-
able. To the best of our knowledge ketoconazole has not been used
as corrosion inhibitor. Thus, the present study aims at determining
the effectiveness of ketoconazole as a corrosion inhibitor by gravi-
metric method as well as by quantum chemical studies.
2. Experimental
Chemical composition of mild steel samples is shown in Table 1.
Specimens used in the weight loss experiment were mechanically
cut into 5.0  4.0  0.8 cm dimensions, then ground with SiC abra-
sive papers 320, 400 and 600 grit, respectively, washed in absolute
ethanol and acetone, dried in room temperature and stored in a
moisture free desiccator before their use in corrosion studies.
0.1 M H2SO4 solutions were prepared by dilution of 97% H2SO4
(Analytical grade) using bidistilled water. Ketoconazole, which
was obtained commercially from May and Baker pharmaceuticals,

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.09.002
 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 198–204
O 3. Results and discussion
N N O
O 3.1. Corrosion rates and inhibition efficiency
O N
H
Cl
Cl
Fig. 1. The chemical structure of ketoconazole. 1-[4-[4-44(2s,4R)-22(2,4-dichloro-
phenyl)-22(imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]phenyl]piperazin-1-yl]-
ethanone.
Table 1
Chemical composition of mild steel samples (wt.%).
C 0.19
Si 0.26
Mn 0.64
P 0.06
S 0.05
Cr 0.08
Mo 0.02
Cu 0.27
Fe Bal.
was added to the acid in concentrations ranging from 2  105 to
1  104 M and the solution in the absence of KCZ was taken as
blank for comparison.
Weight loss tests were conducted under total immersion condi-
tions in 200 ml of test solutions maintained at 30 and 50 °C. The
pre-cleaned and weighed specimens were suspended in beakers
containing the test solutions using glass hooks and rods. All tests
were made in aerated solutions and were run in triplicate. To
determine weight loss with respect to time, the specimens were
retrieved from test solutions at 24-h-interval progressively for
168 h (7 days), immersed in 20% NaOH solution containing 200 g/
l of zinc dust, scrubbed with bristle brush under running water
in order to remove the corrosion product, dried and re-weighed.
The weight loss was taken as the difference between the weight
at a given time and the initial weight of the test coupon deter-
mined using LP 120 digital balance with sensitivity of ±1 mg. The
tests were performed in triplicate to guarantee the reliability of
the results and the mean value of the weight loss is reported.
Weight loss allowed calculation of the mean corrosion rate in
mg cm2 h1.
AM1 (Austin model 1) is a semi-empirical method based on
the neglect of differential diatomic overlap integral approxima-
tion. Specifically, it is a generalization of the modified neglect
of diatomic differential overlap approximation. AM1 was devel-
oped by Michael Dewar and co-workers in 1985. AM1 is an
attempt to improve the MNDO model (Modified neglect of differ-
ential overlap) by reducing the repulsion of atoms at close sep-
aration distances. The atomic core-atomic core terms in the
MNDO equations were modified through the addition of off-cen-
tre attractive and repulsive Gaussian functions. The complexity
of the parameterization problem increased in AM1 as the num-
ber of parameters per atom increased from seven in MNDO to
13–16 per atom in AM1 .The quantum chemical calculation
was performed using Spartan’06 V112 semi-empirical program.
AM1 semi-empirical method was employed to obtain the opti-
mized geometry.
199
The corrosion rates of metals and alloys can be determined
using different electrochemical and non-electrochemical tech-
niques. In this study, gravimetric technique was employed. The
weight loss method of monitoring corrosion rate is useful because
of its simple application and reliability [13]. Several authors have
reported on comparable agreement between weight loss technique
and other techniques of corrosion monitoring. These include polar-
ization measurement [14], hydrogen evolution [15], thermometric
technique [16] and electrochemical impedance spectroscopy [17].
The corrosion of mild steel in 0.1 M H2SO4 solution in the absence
and presence of KCZ was investigated at 30 and 50 °C using weight
loss measurements.
The value of corrosion rate was calculated from the following
equation [7]:
v ¼ ðm1  m2 Þ=St ð1Þ
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 mild steel coupon in (cm2), t is the corrosion time in (h)
and v is the corrosion rate in (mg cm2 h1). The calculated corro-
sion rate (v) in Eq. (1) is an average corrosion rate.
From the corrosion rate, the percentage inhibition efficiency IE%
and the degree of surface coverage (h) were calculated using Eqs.
(2) and (3), respectively [7]:
IE% ¼ ðv 0  v Þ=v 0  100 ð2Þ
h ¼ ðv 0  v Þ=v 0 ð3Þ
where v 0 and v are the corrosion rates of the mild steel coupon in
0.1 M H2SO4 in the absence and presence of KCZ.
A number of mechanistic studies on the anodic dissolution of Fe
in acidic sulphate solutions have been undertaken, and the hydro-
xyl accelerated mechanism proposed initially by Bockris and Draz-
ic [18] and reported by Oguzie [19] has gained overwhelming
acceptance:
Fe þ OH ¡ FeOHads þ Hþ þ e ð4aÞ
rds þ
FeOHads ! FeOH þ e ð4bÞ
þ
FeOH þ H ¡ Fe þ 2þ
þ H2 O ð4cÞ

It has been suggested that anions such as Cl , I , 
SO2 2
and S may
4
also participate in forming reaction intermediates on the corroding
metal surface, which either inhibit or stimulate corrosion [20]. It is
important to recognize that the suppression or stimulation of the
dissolution process is initiated by the specific adsorption of the an-
ion on the metal surface.
A representative plot of weight loss against time (days) for
mild steel in 0.1 M H2SO4 in the absence and present of different
concentrations of ketoconazole at 30 °C is presented in Fig. 2a for
triplicate determination of ketoconazole under identical condi-
tions and Fig. 2b for average determination, respectively. A simi-
lar plot was obtained for 50 °C (not shown). The figures clearly
show a reduction in weight loss of the metal coupons in the pres-
ence of KCZ compared to the blank. Table 2 shows the calculated
values of corrosion rates (mg cm2 h1), inhibition efficiency
(IE%), and the degree of surface coverage h, for mild steel corro-
sion in 0.1 M H2SO4 at 30 and 50 °C. The reproducibility of results
obtained for the percentage inhibition efficiency values for tripli-
cate determination was very precise (±5%). Inspection of the data
reveals that the corrosion rate is higher in the blank (0.1 M
H2SO4) solution than it is in the solution containing KCZ. Also
the corrosion rate is higher at 50 °C than at 30 °C in all cases.
200 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 198–204

0.08 0.06
1 x 10 -4 1 x 10 -4
8 x 10^-5
0.07 8 x 10^-5
6 x 10^-5
4 x 10^-5 0.05 6 x 10^-5
4 x 10^-5
Weight loss (g /cm2)

0.06 2 x 10^-5
Blank ^ 2 x 10^-5
Blank ^

Weight loss (g /cm2)

0.05 0.04

0.04
0.03
0.03

0.02 0.02
0.01
0.01
0
1 2 3 4 5 6 7
Time (days) 0
1 2 3 4 5 6 7
0.08
Time (days)
1 x 10 -4
0.07 8 x 10^-5 Fig. 2b. Plot of weight loss against time (average) for ketoconazole at 30 °C.
6 x 10^-5
4 x 10^-5
0.06 2 x 10^-5
Blank ^ Fe þ H2 O ¡ Fe  H2 Oads ð5aÞ
Weight loss (g /cm2)

0.05 Fe  H2 Oads þ Y ¡ FeOHads þH þY þ

ð5bÞ
Fe  H2 Oads þ Y ¡ FeYads þ H2 O ð5cÞ
0.04 rds
FeOHads ! FeOHads þ e ð5dÞ
0.03 FeYads ¡ FeYþads þ e ð5eÞ
þ
FeOHads þ FeYþads ¡ FeYads þ FeOH ð5fÞ
0.02
FeOHþ þ Hþ ¡ Fe2þ þ H2 O ð5gÞ
0.01
where Y represents the inhibitor species.
0 Considering the inhomogeneous nature of metallic surfaces
1 2 3 4 5 6 7
resulting from the existence of lattice defects and dislocations, a
Time (days) corroding metal surface is generally characterized by multiple
0.05 adsorption sites having activation energies and heats of adsorption.
1 x 10 -4 Inhibitor molecules may thus be adsorbed more readily at surface
0.045 8 x 10^-5
6 x 10^-5
active sites having suitable adsorption enthalpies. According to the
0.04 4 x 10^-5 detailed mechanism above, displacement of some adsorbed water
Weight loss (g /cm2)

2 x 10^-5
0.035 Blank ^ molecules on the metal surface by inhibitor species to yield the ad-
0.03 sorbed intermediate FeYads (Eq. (5c)) reduces the amount of the
species FeOH ads available for the rate-determining steps and conse-
0.025
quently retards Fe anodic dissolution.
0.02
Further inspection of Table 2 clearly shows that the presence of
0.015 KCZ in the solution inhibits the mild steel corrosion and the extent
0.01 of protection efficiency increases with increasing inhibitor concen-
0.005 tration. In contrast, the inhibition efficiency decreases with
increasing temperature. The variation of inhibition efficiency with
0
temperature is a very important tool oftentimes used to deduce the
1 2 3 4 5 6 7
mode of adsorption of inhibitors [23]. For a chemical adsorption
Time (days)
mechanism, the inhibition efficiency increases with increase in
Fig. 2a. Plot of weight loss against time for mild steel corrosion in 0.1 M H2SO4 for temperature while an increase in inhibition efficiency with de-
triplicate determination of ketoconazole prepared under identical conditions at crease in temperature is suggestive of a physical adsorption mech-
30 °C. anism as obtained in this study. Similar observations have been
documented by us [7,31]. Furthermore, the low values of the inhi-
bition efficiency obtained in the present study (Table 2) may be
The increase in corrosion rate with temperature is reasonable and due to the low adsorption and less interference by SO2 4 ion on
is in agreement with that earlier reported by Ebenso [21] that a the mild steel surface as compared to other anion like Cl which
doubling in reaction rate is expected with a 10 °C rise in have a smaller degree of hydration and is expected to be more ad-
temperature. sorbed on the metal surface thus increasing the inhibition effi-
According to the Bockris mechanism outlined earlier, Fe electro- ciency. Similar observations have been documented by El Azhar
dissolution in acidic sulphate solutions depends primarily on the et al. [24] on the study of the inhibitive effect of 2,5-bis (n-pyri-
adsorbed intermediate FeOHads. Ashassi-Sorkhabi and Nabavi-Amri dyl)-1,3-thiadiazoles (n-PTH) on the corrosion of mild steel in
[22] proposed the following mechanism involving two adsorbed 1 M HCl and 0.5 M H2SO4. There is an ongoing research in our lab-
intermediates to account for the retardation of Fe anodic dissolu- oratory to improve the efficiency of ketoconazole using some metal
tion in the presence of an inhibitor: cations and anions.
 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 198–204 201

Table 2
Corrosion parameters for mild steel in 0.1 M H2SO4 in the absence and presence of different concentrations of ketoconazole at 30 and 50 °C.

Temperature (°C) System/concentration Corrosion rate (mg cm2 h1) (IE%) h

30 Blank 0.175 ± 0.3 – –
2  105 M 0.104 ± 0.1 40.45 0.40
4  105 M 0.103 ± 0.1 41.31 0.42
6  105 M 0.101 ± 0.1 42.34 0.42
8  105 M 0.096 ± 0.1 45.20 0.45
1  104 M 0.094 ± 0.2 46.40 0.46
50 Blank 0.286 ± 0.5 – –
2  105 M 0.243 ± 0.2 14.90 0.15
4  105 M 0.235 ± 0.1 17.70 0.18
6  105 M 0.224 ± 0.1 21.70 0.22
8  105 M 0.214 ± 0.2 25.00 0.25
1  104M 0.202 ± 0.2 29.30 0.29

3.2. Adsorption considerations

The primary step in the action of inhibitors in acid solutions is

adsorption onto the metal surface, which is usually oxide-free.
The adsorbed inhibitor then acts to retard the cathodic and/or ano-
dic electrochemical corrosion reaction. It has been reported that
the mechanism of inhibition of an inhibitor may vary with factors
such as concentration, pH, nature of the anion of the acid, and nat-
ure of the metal [25]. Basic information on the interaction between
the inhibitor and the mild steel surface can be provided by the
adsorption isotherm. In order to obtain the isotherm, linear rela-
tion between h values (Eq. (3); Table 3) and inhibitor concentra-
tion, C must be found. Attempts were made to fit the h values to
various isotherms including Langmuir, Temkin, Frumkin and
Flory–Huggins. By far the best fit is obtained with the Langmuir
isotherm. Langmuir adsorption isotherm was found to be the best
description of the adsorption behaviour of the studied inhibitor
among several adsorption isotherms assessed. Langmuir adsorp-
tion isotherm is described by the following equations:
C 1
¼ þC
h K ads
where K ads is the equilibrium constant of the adsorption process, C
the inhibitor concentration.
Fig. 3 shows the dependence of the fraction of the surface cov-
ered C/h as a function of the concentration (C) of ketoconazole. The
obtained plots of the inhibitor are almost linear with a correlation
coefficient higher than 0.94. Though linear plots were obtained, the
deviations of the slope from unity imply that the isotherm may not
be strictly applicable (Table 3). Deviation of the slope from unity
suggests interaction between adsorbed molecules on the metal
surface as well as changes in the adsorption heat with increasing
surface coverage [26–28]. Thus, the adsorption data generally will
be more appropriately described by a modified equation taking the
above factors into consideration. Such a modified Langmuir iso-
therm initially proposed by Villamil et al. [29], has been reported
elsewhere [30]:
C n
¼ þ nC
h K ads
The equilibrium constant of adsorption K ads is related to the stan-
dard free energy of adsorption DG0ads , with the following equation
[8]:
Table 3
Calculated thermodynamic parameters from Langmuir adsorption isotherm.
Kads (M1)
Temperature (°C) DG0ads (kJ/mol) Slope
30 0.68 9.15 4.04
50 0.09 4.21 5.11
Fig. 3. Langmuir adsorption plot for ketoconazole at 30 and 50 °C.
 
1 DGoads
K ads ¼ exp ð8Þ
55:5 RT
ð6Þ
where R is the molar gas constant, T is the absolute temperature and
55.5 is the concentration of water in solution expressed in molar.
Rearranging Eq. (8) gives:
DGoads
log K ads ¼ 1:744  ð9Þ
2:303RT
from where the standard free energy of adsorption can be calcu-
lated. The value of 55.5 is the concentration of water in solution ex-
pressed in mol. The calculated DG0ads and K ads results are listed in
Table 3.
The negative values of DG0ads ensure the spontaneity of the
adsorption process and stability of the adsorbed layer on the mild
steel surface [31]. It is generally accepted that the values of DG0ads
up to 20 kJ/mol are consistent with electrostatic interactions
between the charged molecules and the charged metal (physisorp-
tion) while those around 40 kJ/mol1 or higher are associated
with chemisorption as a result of sharing or transfer of electrons
from organic molecules to the metal surface to form a coordinate
ð7Þ
type of bond (chemisorption) [32]. The values of DG0ads in our mea-
surements was less than 20 kJ/mol, suggesting that KCZ physisor-
ped on mild steel surface. Similar observation was documented by
us recently [33] in the study of synergistic effect and some quan-
tum chemical parameters of 2,3-diaminonapthalene and iodide
ions on the hydrochloric acid corrosion of aluminium at 30 and
40 °C. It could be found that K ads decreased with increasing tem-
R2 perature. This is as a result of the improvement for the desorption
of KCZ from the steel surface suggesting that the inhibitor is
0.99
physically adsorbed on the metal surface. It is well known that
0.95
K ads designates the adsorption power of inhibitor onto the steel
202 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 198–204

surface. Large values of K ads imply more efficient adsorption and
hence better inhibition efficiency while low values imply weak
adsorption and hence low inhibition efficiency as obtained in this
study [34].
3.3. Effects of temperature
Temperature has a great effect on the rate of metal electro-
chemical corrosion. In case of corrosion in a neutral solution (oxy-
gen depolarization) the increase in temperature has a favourable
effect on the overpotential of oxygen depolarization and the rate
of oxygen diffusion but it leads to a decrease of oxygen solubility.
In case of corrosion in an acidic medium (hydrogen depolariza-
tion), the corrosion rate increases exponentially with temperature
increase because the hydrogen evolution overpotential decreases
[35]. An experimental dependence of an integrated Arrhenius-type
equation is observed between the corrosion rate and temperature
[36]:
 
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 [37]:
       tained after geometric optimization with respect to all nuclear
h2 h1 T 1X T 2 1
Q ads ¼ 2:303R log  log x kJ=mol
1  h2 1  h1 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 4.
Some studies [7,15,31,38] showed that compared with the acti-
vation energy, Ea in the absence of inhibitors, higher values of Ea
were found in the presence of inhibitors. Other studies [36,37]
showed that in the presence of inhibitor the activation energy Ea
was lower than that in the absence of inhibitor. In the present study,
however, it could be found that the values of Ea in the presence of dif-
ferent concentrations of KCZ were higher than that in its absence.
This is often interpreted as an indication of the formation of an
adsorptive film of a physical electrostatic character [39]. Thus, the
adsorbed KCZ molecules create a physical barrier to charge and mass
transfer [40]. The negative Q ads values also signify that the degree of
surface coverage decreased with rise in temperature. The reason for
this, as suggested by Oguzie [19], may be that the attainment of
physical adsorption equilibrium is usually rapid and the process
readily reversible whereas in chemisorptions, the occurrence of
chemical reactions at the metal surface makes the process relatively
slow and not readily reversible. Thus, enthalpy changes for chemi-
sorptions are usually higher than for physisorption.
3.4. Quantum chemical calculations
Computational methods have a potential application towards
the design and development of organic corrosion inhibitors in
corrosion field [41]. The studies of Vosta and Eliasek [42] and Chak-
rabarti [43] can be respected as the first theoretical studies on cor-
rosion inhibitors in the literature.
Semi-empirical calculations to evaluate the efficiency of some
imidazole derivatives as acidic corrosion inhibitors for steel have
been performed by Bereket et al. [44] using AM1, PM3, MNDO
and MINDO/3 methods. Charges on nitrogen atoms, total energy,
ionization potential, EHOMO, ELUMO, DE (ELUMO  EHOMO) and dipole
moment (D) were calculated and correlated with experimental re-
sults. A satisfactory agreement was found between theoretical and
experimental data. Similar studies on these compounds have been
carried out by Ogretir et al. [45,46] in order to probe the inhibition
mechanism of corrosion via metal–ligand interaction using semi-
empirical methods. According to their conclusion, semi-empirical
calculations can be used to elucidate the mechanism of inhibition.
Recently we have reported on the inhibition of acid corrosion of Al
in HCl using fluconazole and 2,3-diaminonaphthalene using both
experimental and semi-empirical quantum studies at the AM1 le-
vel of theory [7,31]. Results obtained using this level of theory
ð10Þ was satisfactory.
Table 5 shows some of the key quantum chemical parameters
computed using AM1 method. These are mainly the energies of
the highest occupied (EHOMO) and lowest unoccupied (ELUMO)
molecular orbitals, energy of the gap, DE (ELUMO  EHOMO) and di-
pole moment (D). These quantum chemical parameters were ob-
coordinates.
Frontier orbital theory is useful in predicting adsorption centres
ð11Þ of the inhibitor molecules responsible for the interaction with sur-
face metal atoms [47]. Moreover, the gap between the LUMO and
HOMO energy levels of the molecules was another important fac-
tor that should be considered. It has been reported that excellent
corrosion inhibitors are usually those organic compounds who
are not only offer electrons to unoccupied orbital of the metal,
but also accept free electrons from the metal [48]. It is also well
documented in literature that the higher the HOMO energy of
the inhibitor, the greater its ability of offering electrons to unoccu-
pied d-orbital of the metal, and the higher the corrosion inhibition
efficiency. In addition, the lower the LUMO energy, the easier the
acceptance of electrons from metal surface, as the LUMO–HOMO
energy gap decreased and the efficiency of inhibitor improved.
Quantum chemical parameters listed in Table 4 reveal that KCZ
has high HOMO and low LUMO with high energy gap. Similar
observations have been reported by Khaled [41] on the adsorption
and inhibitive properties of a new synthesized guanidine deriva-
tive on corrosion of copper in 0.5 M H2SO4.
According to Pearson [49], when two systems Fe and inhibitors
are brought together electrons will flow from lower v (inhibitor) to
higher v (Fe) until the chemical potentials become equal. As a first
approximation, the fraction of electron transferred, DN, is given by:
vFe  vinb
DN ¼ ð12Þ
2ðgFe þ ginh Þ
Table 5
Quantum chemical parameters for KCZ.

Calculated parameters for KCZ Value

Table 4
Calculated values of activation energy (Ea) and heat of adsorption (Q ads ) for mild steel Heat of formation (kJ/mol) 387.58
dissolution in 0.1 M H2SO4 in the absence and presence of KCZ at 30 and 50 °C. EHOMO (eV) 8.42105425
ELUMO (eV) 0.22989375
System/concentration Ea (kJ/mol1) Q ads (kJ/mol1) DE (ELUMO  EHOMO) (eV) 8.19116050
Dipole moment (D) 3.906
Blank 19.95 –
Ionization potential (eV) 8.42105425
2  105 M 34.49 37.17
Electron affinity (eV) 0.22989375
4  105 M 33.71 32.23
Molecular weight (amu) 508.446
6  105 M 32.36 26.37 0
514.133
8  105 M 32.88 25.11 A)
CPK area (Å
1  104 M 31.19 20.56 DN 0.326
 I.B. Obot, N.O. Obi-Egbedi / Corrosion Science 52 (2010) 198–204
where vFe and vinh denote the absolute electro-negativity of Fe and
the inhibitor molecule, respectively; gFe and ginh denote the abso-
lute hardness of Fe and the inhibitor molecule, respectively. From
Eq. (4), the Fe is the lewis acid according to HSAB (Hard and Soft
Acid and Base) theory [50]. The difference in electro-negativity
drives the electron transfer, and the sum of the hardness parame-
ters acts as a resistance [49]. These quantities are related to electron
affinity (A) and ionization potential (I) which are useful in their abil-
ity to help predict chemical behaviour [51].
IþA
v¼ ð13Þ
2
IA
g¼ ð14Þ
2
I and A are related in turn to EHOMO and ELUMO as follows:
I ¼ EHOMO ð15Þ
A ¼ ELUMO ð16Þ
Values of v and g were calculated by using the values of I and A ob-
tained from quantum chemical calculations. Using a theoretical v
value of 7 eV/mol according to pearsons electro-negativity scale
[49] and a global hardness g value of 0 eV/mol for Fe by assuming
that for a metallic bulk I = A [52], DN, which is the fraction of elec-
trons transferred from inhibitor to the mild steel surface was calcu-
lated (Table 5). Values of DN showed inhibition effect resulted from
electrons donation. According to Lukovits [53], if DN <3.6, the inhi-
bition efficiency increased with increasing electron donating ability
at the metal surface. In this study, KCZ was the donor of electrons,
and the mild steel surface was the acceptor. This result supports the
assertion that the adsorption of inhibitor on the metal surface can
occur on the bases of donor- acceptor interactions between the p
electrons of the heterocyclic compound and the vacant d-orbitals
of the metal surface [54].
3.5. Mechanism of inhibition of ketoconazole on the mild steel surface
As noted earlier, 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; the presence of a metal
having vacant low-energy electron orbital and of an inhibitor with
molecules having relatively loosely bound electrons or heteroatom
with lone pair electrons. Thus in the sulphuric acid medium, KCZ
may be protonated predominantly affecting the nitrogen atoms
[31]. Thus, they become cations, existing in equilibrium with the
corresponding molecular form:
KCZ þ 2Hþ $ ½KCZ2þ ð17Þ
The protonated KCZ, however, could be attached to the mild steel
surface by means of electrostatic interaction between SO2 4 and pro-
tonated KCZ since the steel surface has positive charges in the acid
medium [55]. This could further be explained based on the assump-
tion that in the presence of SO2 2
4 , the negatively charged SO4 would
attach to positively charged surface. When KCZ adsorbs on the steel
surface, electrostatic interaction takes place by partial transference
of electrons from the polar atom (N and O atoms and the delocal-
ized p electrons around the heterocyclic rings) of KCZ to the metal
surface. In addition to electrostatic interaction (physisorption) of
KCZ molecules on the steel surface, molecular adsorption may also
play a role in the adsorption process. Thus we predict that the
adsorption of ketoconazole on the steel surface in sulphuric acid
may be achieved by the interaction between iron atoms and cyclic
molecular p orbital. The electronic configuration of iron is
[Ar]4s23d6, 3d orbital is not fully filled with electrons. The unfilled
orbital of iron could bond with the highest occupied molecular orbi-
tal (HOMO) [56] of KCZ, while the filled 4s orbital of the former
203
could interact with the lowest unoccupied molecular orbital
(LUMO) of the latter. Similar interaction has been reported
[57,24,58].
4. Conclusions
1. Results obtained from the experimental data shows that keto-
conazole acts as inhibitor for the corrosion of mild steel in
0.1 M H2SO4.
2. Inhibition efficiency increases with increase in the concentra-
tion of the studied inhibitor but decreases with rise in
temperature.
3. The adsorption of KCZ on mild steel surface from 0.1 M H2SO4
obeys the Langmuir adsorption isotherm.
4. Phenomenon of physical adsorption is proposed from the values
of (Ea, Q ads , DG0ads ) obtained.
5. The adsorption of KCZ onto mild steel surface was a spontane-
ous process.
6. Quantum chemical calculations show that apart from KCZ mol-
ecules adsorbing as cationic species on the mild steel surface, it
can also adsorbed as molecular species using oxygen, nitrogen
and the p electrons of the aromatic ring as its active centres.
7. The relationship between the inhibition efficiency of KCZ on
mild steel in 0.1 M H2SO4 and the EHOMO, EHOMO  ELUMO, and
DN of KCZ were calculated by AM1 method and discussed.
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